UniSIm Manual

Uni Si m Desi gn
Si mul at i on Basi s
Ref er ence Gui de
Copy r i ght
November 2010 R400 Release
The informat ion in t his help file is subj ect t o change over t ime. Honeywell may make
changes t o t he requirement s described. Fut ure revisions will incorporat e changes, including
correct ions of t ypographical errors and t echnical inaccuracies.
For furt her informat ion please cont act
Honeywell
300- 250 York St reet
London, Ont ario
N6A 6K2
Telephone: ( 519) 679- 6570
Facsimile: ( 519) 679- 3977
Copyright Honeywell 2010. All right s reserved.
Prepared in Canada.
v
Table of Cont ent s
Uni Si m Desi gn Ther mody nami cs . . . . . . . . . . . . . . . . . . . . . . . . . . . . v i i
1 Component s ....... ........ ....... ....... ........ ....... ....... ...... 1- 1
1. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1- 2
1. 2 Component List View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1- 4
2 Fl ui d Pack age ..... ........ ....... ....... ........ ....... ....... ...... 2- 1
2. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2- 2
2. 2 Fluid Packages Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2- 2
2. 3 Adding a Fluid Package - Example . . . . . . . . . . . . . . . . . . . . . . 2- 4
2. 4 UniSim Design Fluid Package Propert y View . . . . . . . . . 2- 6
2. 5 UniSim Thermo Propert y View. . . . . . . . . . . . . . . . . . . . . . . . . . 2- 84
2. 6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2- 104
3 Hy pot het i cal s ..... ........ ....... ....... ........ ....... ....... ...... 3- 1
3. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 3
3. 2 Hypo Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 3
3. 3 Adding a Hypot het ical - Example . . . . . . . . . . . . . . . . . . . . . . . . 3- 5
3. 4 Creat ing a Hypo Group. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 11
3. 5 Hypot het ical Component Propert y View . . . . . . . . . . . . . 3- 21
3. 6 Solid Hypot het icals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 28
3. 7 Cloning Library Component s . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 33
3. 8 Hypo Cont rols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 34
3. 9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3- 36
4 Uni Si m Desi gn Oi l Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 1
4. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 3
4. 2 Oil Charact erizat ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 4
4. 3 Pet roleum Fluids Charact erizat ion Procedure . . . . . . . . 4- 8
4. 4 Oil Charact erizat ion View. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 11
4. 5 Charact erizing Assays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 14
4. 6 Hypocomponent Generat ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 47
4. 7 User Propert y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 61
4. 8 Correlat ions & I nst allat ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 64
4. 9 TBP Assay - Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 71
4. 10 Sulfur Curve - Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 84
vi
4. 11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4- 90
5 React i ons .... ....... ........ ....... ....... ........ ....... ....... ...... 5- 1
5. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 2
5. 2 React ion Component Select ion . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 2
5. 3 React ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 5
5. 4 React ion Set s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 29
5. 5 Generalized Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 38
5. 6 React ions - Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5- 39
6 Component Maps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6- 1
6. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6- 2
6. 2 Component Maps Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6- 2
6. 3 Component Map Propert y View. . . . . . . . . . . . . . . . . . . . . . . . . . . 6- 3
7 User Pr oper t i es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7- 1
7. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7- 2
7. 2 User Propert y Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7- 3
7. 3 User Propert y View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7- 4
8 PVT Env i r onment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8- 1
8. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8- 2
8. 2 PVT Environment Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8- 3
8. 3 Simulat ion Basis Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8- 5
8. 4 St ream Propert y View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8- 6
9 BI P Opt i mi zer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 1
9. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 2
9. 2 BI P Opt imizer View. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 2
9. 3 Variables Tab. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 3
9. 4 Funct ions Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 4
9. 5 Paramet ers Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 5
9. 6 Monit or Tab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 7
9. 7 BI P Opt imizer Tips. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 8
9. 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9- 9
A Pr oper t y Met hods & Cal cul at i ons . . . . . . . . . . . . . . . . . . . . . . . . . . A- 1
A. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A- 3
A. 2 Select ing Propert y Met hods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A- 4
A. 3 Propert y Met hods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A- 8
A. 4 Ent halpy & Ent ropy Depart ure Calculat ions . . . . . . . . A- 46
A. 5 Physical & Tr ansport Propert ies . . . . . . . . . . . . . . . . . . . . . . . . A- 52
A. 6 Volumet ric Flow Rat e Calculat ions . . . . . . . . . . . . . . . . . . . . A- 60
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A. 7 Flash Calculat ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A- 65
A. 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A- 75
B Oi l Met hods & Cor r el at i ons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B- 1
B. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B- 2
B. 2 Charact erizat ion Met hod. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B- 2
B. 3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B- 9
C Ami nes Pr oper t y Pack age .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 1
C. 1 Amines Propert y Package . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 2
C. 2 Non- Equilibrium St age Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 5
C. 3 St age Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 6
C. 4 Equilibrium Solubilit y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 9
C. 5 Phase Ent halpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 17
C. 6 Simulat ion of Amine Plant Flowsheet s . . . . . . . . . . . . . . . C- 17
C. 7 Progr am Limit at ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 21
C. 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C- 21
D Gl y col Pr oper t y Pack age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D- 1
D. 1 I nt roduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D- 2
D. 2 Pure Component Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . D- 3
D. 3 Mixing Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D- 4
D. 4 Phase Equilibrium Predict ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D- 9
D. 5 Ent halpy/ Ent ropy Calculat ions. . . . . . . . . . . . . . . . . . . . . . . . . . D- 10
D. 6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D- 10
I ndex .... ....... ....... ........ ....... ....... ........ ....... ....... ...... I - 1
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UniSim Design
Thermodynamics
To comprehend why UniSim Design is such a powerful engineering
simulat ion t ool, you need look no furt her t han it s st rong
t hermodynamic foundat ion. The inherent flexibilit y cont ribut ed t hrough
it s design, combined wit h t he unparalleled accuracy and robust ness
provided by it s propert y package calculat ions leads t o t he
represent at ion of a more realist ic model.
Not only can you use a wide variet y of int ernal pr oper t y packages, you
can use t abular capabilit ies t o override specific propert y calculat ions for
more accuracy over a narrow range or use t he funct ionalit y provided
t hrough Act iveX t o int eract wit h ext ernally const ruct ed propert y
packages. Through t he use of Ext ensibilit y, you can ext end UniSim
Design so t hat it uses propert y packages t hat you cr eat ed wit hin t he
UniSim Design environment .
The built - in propert y packages provide accurat e t hermodynamic,
physical, and t ransport pr opert y predict ions for hydrocarbon, non-
hydrocarbon, pet rochemical, and chemical fluids.
The Thermodynamics development group at Honeywell has evaluat ed
experiment al dat a from t he worlds most respect ed sources. Using t his
experiment al dat a, a dat abase cont aining in excess of 1500
component s and over 16, 000 fit t ed binaries has been creat ed. I f a
library component cannot be found wit hin t he dat abase, a
comprehensive select ion of est imat ion met hods is available for cr eat ing
fully defined hypot het ical component s.
A component propert y dat abase loader st ruct ure has been developed at
Honeywell for loading component propert ies like component
descript ors, propert y const ant s, and t emperat ure dependent propert ies
from ot her dat abases such as DI PPR dat abase. This feat ure allows user
t o load infor mat ion from any component propert y dat abase, including
UniSim user dat abase t hrough a COM based loader.
UniSim Design also cont ains a powerful regression package t hat may
be used in conj unct ion wit h it s t abular capabilit ies. Experiment al pure
component dat a, which UniSim Design pr ovides for over 1, 000
Pl ease cont act Honey w el l f or f ur t her i nf or mat i on on how t o
bui l d i nt er f aces t o y our ow n component dat abases.
v i i i
viii
component s, can be used as input t o t he regression package.
Alt ernat ively, you can supplement t he exist ing dat a or supply a
complet e set of your own dat a. The regression package fit s t he input
dat a t o one of t he numerous mat hemat ical expressions available in
UniSim Design. This allows you t o obt ain simulat ion result s for specific
t hermophysical proper t ies t hat closely mat ch your experiment al dat a.
As new t echnology becomes available t o t he market place, Honeywell
welcomes t he changes. UniSim Design was designed wit h t he foresight
t hat soft ware t echnology is ever- changing and t hat a soft ware product
must reflect t hese changes. UniSim Design has incorporat ed UniSim
Thermo which is an advanced t hermodynamic calculat ion framework
based on Microsoft s COM ( Component Obj ect Model) t echnology. The
UniSim Thermo framework is fully component ized which makes it
possible t o develop independent , ext ensible, cust omizable, and
encapsulat ed t hermodynamic calculat ion modules. I t act s like a
t hermodynamic calculat ion server which allows users t o ut ilize,
supplement , or replace any of it s component s.
The framewor k also encompasses a wide variet y of proper t y
calculat ions, flash met hods, dat abases, et c. The calculat ion met hods
cover all of t he t hermodynamic calculat ion packages in UniSim Design.
I n fut ure releases of UniSim Design, t he old UniSim Design
t hermodynamic engine will gradually be replaced by UniSim Thermo.
Simulat ion Basis Manager
One of t he import ant concept s upon which UniSim Design is based is
t hat of environment s. The Basis Environment allows you t o input or
access informat ion wit hin t he Simulat ion Basis Manager while t he ot her
areas of UniSim Design are put on hold. This helps t o maint ain peak
efficiency by avoiding unnecessary flowsheet calculat ions. Once you
ret urn t o t he Build Environment , all changes t hat were made in t he
Basis Environment t ake effect at t he same t ime. Conversely, all
t hermodynamic dat a is fixed and is not changed as manipulat ions t o t he
flowsheet t ake place in t he Build Environment .
Use t he Hot Key CTRL B t o
re- ent er t he Basis
Environment from any
Environment .
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ix
Anot her advant age of t he Simulat ion Basis Environment is t he
assurance t hat all t he basic t hermodynamic requirement s are provided
before a simulat ion case is built . The minimum informat ion required
before leaving t he Simulat ion Basis Manager is as follows:
At least one inst alled fluid package wit h an at t ached Propert y
Package.
At least one component in t he fluid package.
A fluid package specified as t he Default fluid package. This is
aut omat ically done by UniSim Design aft er t he first fluid
package is inst alled.
The Simulat ion Basis Manager can be accessed at any st age during t he
development of a simulat ion case. When a New Case is creat ed, t he
first view t hat appears is t he Simulat ion Basis Manager. You can also
ret urn t o t he Basis Environment from t he Main or Sub- Flowsheet
Environment at any t ime t o make changes t o t he t hermodynamic
informat ion.
You can creat e as many fluid packages as you like in t he Simulat ion
Basis Manager. This funct ionalit y makes it possible for each flowsheet in
t he case t o be associat ed wit h an individual fluid package, t hus allowing
it t o have it s own part icular pr opert y package and set of component s.
The Default fluid package is assigned t o each new Sub- Flowsheet t hat
is creat ed while in t he Build Environment . I f a different fluid package is
desired, you can re- ent er t he Basis Environment t o perform t he
required change.
Provided t hat changes are made in t he Basis Environment , UniSim
Design displays a message box each t ime you re- ent er t he Main Build
Environment .
This provides a means of leaving UniSim Design in HOLDI NG mode so
t hat you can perform compliment ary changes ( i. e., new st ream
composit ions, column specificat ions) t o t he flowsheet prior t o t he Basis
modificat ions t aking effect .
The Simulat ion Basis Manager proper t y view allows you t o creat e and
manipulat e fluid packages in t he simulat ion. Whenever you cr eat e a
New Case, UniSim Design opens t o t he Component s t ab of t he
Fi gur e 1. 1
I f UniSim Design is left in
HOLDI NG mode,
calculat ions can be
act ivat ed by clicking t he
Solver Act ive icon in t he
Toolbar.
For more
informat ion about
t he Simulat ion Basis
Manager view, refer
t o Sect i on 5. 2 -
Manager from t he
Uni Si m Desi gn
User Gui de.
x
x
Simulat ion Basis Manager.
The t abs available on t he Simulat ion Basis Manager view are described
in t he t able below:
Fi gur e 1. 2
Tab Descr i pt i on
Component s Allows access t o a component list which is associat ed
wit h a fluid package. When adding a new component
list or edit ing a current list , t he Component List View
opens. This view is designed t o simplify adding
component s t o t he case.
Fl ui d Pk gs Allows you t o creat e and manipulat e all fluid packages
for t he simulat ion case. Also, you can assign a fluid
package t o each flowsheet t hat exist s wit hin t he case
and select a Default fluid package, which is
aut omat ically used for all new flowsheet s.
Hy pot het i cal s Allows individual Hypot het icals and Hypot het ical
Groups t o be defined for inst allat ion int o any fluid
package.
Oi l Manager Allows access t o t he Oil Environment where you can
input assay dat a, cut / blend an oil and define pseudo
component s for inst allat ion in any exist ing fluid
package.
React i ons Allows you t o inst all react ion component s, creat e
react ions, creat e react ion set s, at t ach react ions t o
react ion set s and at t ach react ion set s t o any exist ing
fluid package.
Component Maps Allows you t o specify composit ion across fluid package
( subflowsheet ) boundaries.
User Pr oper t y Creat e and make user propert ies available t o any fluid
package.
The Ent er Si mul at i on
Env i r onment but t on can
be accessed from any of
t he t abs on t he
Simulat ion Basis Manager
view.
Component s 1- 1
1- 1
1 Component s
1.1 I nt r oduct i on ............. ........................................................... .......... 2
1.2 Component Li st Vi ew ........................................................... .......... 4
1.2.1 Adding Library Component s.. .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 5
1.2.2 Select ing Library Component s. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
1.2.3 Manipulat ing t he Select ed Component s List . ... .. ... .. .. ... .. ... .. .. ... .. .. 13
1.2.4 Adding Elect rolyt e Component s. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 28
1.2.5 Adding Hypot het ical Component s . .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 29
1.2.6 Adding Component s from Exist ing Component List s .. ... .. ... .. .. ... .. .. 31
1- 2 I nt r oduct i on
1- 2
1. 1 I nt roduct ion
The Component s Manager is accessed by select ing t he Component s t ab
from t he Simulat ion Basis Manager. The Component s Manager provides
a locat ion where set s of chemical component s being modeled may be
ret rieved and manipulat ed. These component set s are st ored in t he
form of Component List s which may be a collect ion of library pure
component s or Hypot het ical component s.
The Component s Manager always cont ains a Mast er Component List
t hat cannot be delet ed. The Mast er Component List cont ains every
component available fr om all component list s. I f you add component s
t o any ot her Component List , t hey are aut omat ically added t o t he
Mast er Component List . Also, if you delet e a component from t he
mast er, it is delet ed fr om any ot her Component List t hat is using it .
When working wit h t he Fluid Package Manager, component s are
associat ed wit h Fluid Packages t hrough Component List s. A Component
List must be select ed for each Fluid Package creat ed. For furt her det ails
regarding t o t he use of Component List s wit h Fluid Packages, see
Chapt er 2 - Fl ui d Pack age.
Fi gur e 1. 1
You cannot associat e t he
Mast er Component List t o
a fluid package. Add a
component list and
associat e it t o a fluid
package.
Component s 1- 3
1- 3
The Component s t ab of t he Simulat ion Basis Manager view cont ains six
but t ons which allow you t o organize all component list s for t he current
case. Each but t on is described in t he following t able:
But t on Descr i pt i on
Vi ew Opens t he Component List view for t he select ed Component
List . From t his view, you can add, modify, or remove
individual component s from t he current list .
Add Allows you t o add a new Component List int o t he case.
When clicked, t he Component List view appears and
component s associat ed wit h t he case may be added. New
component s may be added t o t he component list by
highlight ing t he component list name and clicking t he View
but t on.
Del et e Allows you t o delet e a Component List from t he case. No
warning message is provided before delet ing a list and a
delet ed Component List cannot be recovered.
Copy Makes a copy of t he select ed ( highlight ed) Component List .
The copied version is ident ical t o t he original, except for t he
name. This command may be useful for modifying
Component List s while keeping t he original list int act .
I mpor t Allows you t o import a pre- defined Component List from a
disk. When t he I mport but t on is select ed, t he locat ion
dialog window for t he component list file appears.
Component List s have a file ext ension of ( * . cml ) .
Ex por t Allows you t o export t he select ed Component List s ( * . cml )
t o disk. The export ed list file can be ret rieved in anot her
case by using t he I mport funct ion det ailed above.
Ref r esh Allows you t o reload component dat a from t he dat abase.
For example, if you have a case from a previous version,
t he dat a is updat ed from t he older version t o t he lat est
version.
Re- i mpor t Allows you t o updat e select ed component list from disk.
When t he Re- import but t on is select ed, t he locat ion dialog
window for t he component list file appears. Component list s
have a file ext ension of ( * . cml) . The re- import ed and
select ed for updat e component list s are expect ed t o have
t he same number of ident ically named component s.
1- 4 Component Li st Vi ew
1- 4
1. 2 Component List View
When adding or viewing an exist ing Component List fr om t he
Component s t ab of t he Simulat ion Basis Manager view, t he Component
List View is opened.
The Component List View is designed t o simplify adding component s t o
a Component List . Access is pr ovided t o all Library component s wit hin
UniSim Design, which include t he t radit ional component s, elect rolyt es,
defined Hypot het icals, and ot her exist ing list s. The view consist s of t he
following t abs:
The Select ed t ab allows you t o add component s and view t heir
propert ies. The Component s page view varies according t o t he
t ree configurat ion select ion in t he Add Component group.
Fi gur e 1. 2
The Name cell displays t he name of
t he component list being viewed.
The Add Component t ree configurat ion allows you
t o filt er t hrough alt ernat ive component list s.
Component s 1- 5
1- 5
The Component by Type t ab displays all component s select ed for
t he component list by it s part icular t ype ( t radit ional,
elect rolyt es, hypot het icals, et c. ) as shown below.
"The Component Dat abases t ab let s you t o manage component
propert y dat abases by adding, removing, reset t ing or ordering
Component Propert y Dat abases. The component propert y
dat abase order will decide t he set of available component s in
t he component list .
1. 2. 1 Adding Library Component s
The Component List View shown pr eviously is encount ered when you
are adding Library component s t o a Component List . Use t he Add
Fi gur e 1. 3
Fi gur e 1. 4
1- 6
Component t ree configurat ion t o filt er t he library component s for each
group list ed.
The Select ed t ab view has t hree main groups:
t he Add Component t r ee
Select ed Component s group
Component s Available in t he Component Library group.
Each group is described separat ely in t he following sect ions.
Add Component Tree
The Add Component group allows you t o filt er component s by t ype.
Select ing component s from t he component t ree det ermines t he t ype of
component s t hat are displayed in t he Component s Available in
Component Library group. A different view is displayed depending on
whet her you are adding Tradit ional, Elect rolyt es, Hypot het ical, or Ot her
component s.
Select ed Component s Group
The Select ed Component s group shows t he list of component s t hat
have been added.
The various funct ions t hat allow you t o manipulat e t he list of select ed
component s are list ed in t he following t able:
Fi gur e 1. 5
Obj ect Descr i pt i on
Sel ect ed
Component s
Cont ains all t he current ly inst alled component s for a
part icular component list .
Add Pur e Adds t he highlight ed component ( s) from t he
Component s Available group t o t he Select ed
Component s list .
Add Component t ree
browser
Component s 1- 7
1- 7
Component s Available in t he Component
Library Group
The Component s Available in t he Component Library group displays
library component s depending on t he filt ered met hod used.
Subst i t ut e Swaps t he highlight ed select ed component s wit h t he
highlight ed available component .
Remov e Comp Delet es t he highlight ed component from t he Select ed
Component s list .
Sor t Li st Accesses t he Move Component s view, where you can
change t he order of t he select ed component list .
Vi ew Component Accesses t he select ed component s ident ificat ion
propert y view.
When subst i t ut i ng component s, Uni Si m Desi gn r epl aces t he
component t hr oughout t he case ( i .e. , al l speci f i cat i ons f or
t he ol d component ar e t r ansf er r ed t o t he new component ) .
How ever , t he subst i t ut i on f unct i on does not aut omat i cal l y
handl e component s t hat ar e par t of a React i on.
Fi gur e 1. 6
1- 8
The group has several feat ures designed t o make t he select ion of
component s as efficient and convenient as possible.
1. 2. 2 Select ing Library
Component s
As ment ioned pr eviously, library component s are select ed from t he
Component s Available in t he Component Library group, and placed in
t he Select ed Component s group. There are many ways in which you can
select component s for a component list . Once you become familiar wit h
t he available met hods for component select ion, you can select t he
procedure t hat you find most convenient .
The process of adding component s fr om t he component library t o t he
Select ed Component s list can be divided int o t hree sub- processes. By
visualizing t he process of component select ion in t his way, you are
made aware of all t he available possibilit ies offered by UniSim Design.
You can t hen adopt t he most logical and efficient appr oach t o use each
t ime you build a case.
For component addit ion t o t he component list , t he following met hods
are recommended:
1. Filt er t he library list .
2. Select t he desired component ( s) .
3. Transfer t he component ( s) t o t he Select ed Component s list .
Mat ch As you t ype in t his cell, UniSim Design filt ers t he
component list t o locat e t he component t hat best
mat ches your current input . This depends on t he radio
but t on select ed.
Vi ew Fi l t er s This but t on opens t he Filt ers float ing view which
cont ains a range of propert y packages and component
filt ering opt ions t o assist in your component select ion
process.
Si mName
Ful l Name/
Sy nonym
For mul a
These t hree radio but t ons det ermine t he cont ext of
your input in t he Mat ch cell.
Show Synonyms When t his checkbox is act ivat ed UniSim Design
includes known synonyms for each component in t he
list .
Cl ust er This checkbox is available only when t he Show
Synonyms checkbox is checked. By checking t he
Clust er checkbox, all synonyms are indent ed and list ed
below t he component name. Ot herwise, t he synonyms
are list ed alphabet ically t hroughout t he list .
For furt her det ails, refer
t o Fi l t er Opt i ons f or
Tr adi t i onal
Component s.
Whenever a
component ( s) is
highlight ed in t he
Available List , click t he
Add Pure but t on t o
move it t o t he Select ed
Component List .
Component s 1- 9
1- 9
Filt ering t he Component List for
Tradit ional Component s
A recommended pract ice for component select ion is t he use of t he
available t ools which UniSim Design provides for filt ering t he
component library. This narrows t he select ion range and allows you t o
apply one of t he various met hods for t ransferring t he select ion( s) t o t he
Select ed Component s list .
Filt ering opt ions for elect rolyt es and hypot het icals are different and
available in Sect i on 1.2.4 - Addi ng El ect r ol y t e Component s and
Sect i on 1. 2. 5 - Addi ng Hy pot het i cal Component s, respect ively.
There are four t ools available for filt ering t he list in t he Component s
Available in t he Component Library group. The filt ering t ools can be
used independent ly or in combinat ion and are described in t he t able
below:
When t rying t o Mat ch a component , UniSim Design searches t he
component column in t he list for whichever radio but t on is select ed:
By using t he Mat ch input cell, you can access any component wit hin t he
UniSim Design library t hat is accessible under t he current ly select ed
Propert y Package. You can make t he Mat ch field act ive by select ing it or
by using t he ALT M hot key.
Fi l t er i ng Tool Descr i pt i on
Pr oper t y Pack age &
Fami l y Ty pe Fi l t er s
Filt ers t he list according t o your select ion of
propert y package and/ or component families.
Refer t o previous Fi l t er Opt i ons f or Tr adi t i onal
Component s for furt her det ails.
Show Synonyms Component synonyms appear alphabet ically
t hroughout t he list when t his checkbox is
act ivat ed.
Cl ust er The Clust er checkbox is available only when t he
Show Synonyms checkbox is act ivat ed and Mat ch
input field is empt y. By act ivat ing t he Clust er
checkbox, all synonyms are indent ed and list ed
below t he component name.
Mat ch This input cell allows t ype- mat ching of t he
component simulat ion name, full name, synonym
or formula.
Radi o But t on Descr i pt i on
Si mName This opt ion mat ches t he t ext ent ered int o t he Mat ch input
t o t he name used wit hin t he simulat ion.
Ful l Name/
Sy nonym
This opt ion may mat ch t he component s full name or a
synonym of t he SimName. I t is t ypically a longer name.
For mul a Use t his opt ion when you are not sure of t he library name,
but know t he formula of t he component .
1- 10
The Mat ch input cell accept s keyboard input , and is used by UniSim
Design t o locat e t he component in t he current list which best mat ches
your input . The first charact er of t he filt ered component names must
agree wit h first charact er of t he list ed component name. Subsequent
charact ers in t he Mat ch cell must appear somewhere in each list ed
component name. Ot her t han t he first charact er, any number of
unmat ched charact ers can appear wit hin t he names of t he list ed
component s.
I f t he component you want t o add is Wat er, t ype H2 in t he Mat ch cell.
UniSim Design filt ers t he list of available Library Component s t o only
t hose t hat mat ch your current input st ring. The fir st component in t he
list , H2, is an exact mat ch of your curr ent input and t her efore, is
highlight ed. Not ice t hat H2O is available in t he list even t hough you
have ent ered only H2.
Since Hydrogen is not t he component of choice, you can cont inue t o
reduce t he list of available library component opt ions by t yping in t he
charact er O aft er t he H2 in t he Mat ch cell.
Fi gur e 1. 7
Component s 1- 11
1- 11
Filt er Opt ions for Tradit ional
Component s
The float ing Filt er view is accessed by clicking t he View Filt ers but t on
from Component List View. I t allows access t o t he Propert y Package
filt er and Family Type filt er opt ions.
The Propert y Package Filt er group filt ers component s based on t heir
compat ibilit y wit h t he select ed propert y package. Once a propert y
package is select ed, t he Recommended Only checkbox works as
follows:
I f t he Recommended Only checkbox is select ed, UniSim Design
only displays ( in t he component library list ) component s t hat
are recommended wit h t he chosen propert y package.
I f t he Recommended Only checkbox remains unselect ed, all t he
component s in t he UniSim Design library are displayed in t he
component library list . An x is shown beside each component
t hat UniSim Design does not recommend for t he select ed
propert y package. However, you may st ill select t hese
component s if you want .
The Family Type Filt er group allows UniSim Design t o filt er t he list of
available component s t o only t hose belonging t o a specific family. The
Use Filt er checkbox t oggles t he Family Type Filt er opt ions On and Off.
By default , all checkboxes in t he Family Filt er group are deact ivat ed.
You can ident ify which families should be included in t he list of available
component s by select ing t he desired checkbox( es) . The All but t on
act ivat es all checkboxes, and t he I nvert but t on t oggles t he st at us of
each checkbox individually. For example, if you act ivat e all of t he
checkboxes, and t hen want t o quickly deact ivat e t hem, simply click t he
I nvert but t on. I f you only had t he Hydrocarbons and t he Solids opt ions
act ivat ed and you clicked t he I nvert but t on, t hese t wo opt ions are
deact ivat ed and t he remaining opt ions are act ivat ed.
The Pr oper t y Pack age Fi l t er i s onl y a component sel ect i on
f i l t er i ng t ool and does not associ at e a Fl ui d Pack age w i t h t he
component l i st ( t hi s i s accompl i shed w i t hi n t he Fl ui d
Pack age Manager ) .
1- 12
Select ing t he Component ( s)
Aft er t he list of Library Component s ar e filt ered, you can see t he
desired component among t he displayed component s. Use one of t he
following available met hods t o highlight t he component ( s) of choice
described in t he following t able:
Whenever t he list of component s is filt ered, t he highlight is placed on
t he first component in t he reduced list . I f you use t he keyboard
commands t o access t he list of component s, you may have t o move t he
highlight if t he first component is not desired.
To move t hrough t he Component s Available in t he Component Library
group, use one of t he following met hods:
Transferring t he Component ( s)
Aft er t he Library Component list is filt ered and t he desired
component ( s) highlight ed, t ransfer t he select ion( s) t o t he Select ed
Component s list . Use one of t he following met hods:
Click t he Add Pur e but t on
Press t he ENTER key
Double- click on t he highlight ed it em. This opt ion only works for
a single component select ion.
The met hods are t he same whet her you are adding t radit ional
component s, elect rolyt es, hypot het icals, or ot her component s.
Sel ect i on Met hod Descr i pt i on
Mouse Place t he cursor over t he desired component and press
t he primary mouse but t on.
Key boar d Use t he TAB key or SHI FT TAB combinat ion t o move
t he act ive locat ion int o t he list of component s.
Met hod Descr i pt i on
Ar r ow Keys Move t he highlight up or down one line in t he
component list .
Page Up/ Page
Dow n
Use t hese keyboard keys t o move t hrough t he list an
ent ire page at a t ime.
Home/ End The HOME key moves t o t he st art of t he list and t he
END key moves t o t he end of t he list .
Scr ol l Bar Wit h t he mouse, use t he scroll bar t o navigat e t hrough
t he list .
Component s 1- 13
1- 13
1. 2. 3 Manipulat ing t he Select ed
Component s List
Aft er adding t he component s t o t he Select ed Component s list , you can
subst it ut e, remove, sort and view component s. These met hods apply t o
t radit ional library component s, elect r olyt es, hypot het icals, and ot her
component s.
To demonst rat e t he manipulat ion funct ions, t he Select ed Component s
group shown below is used for reference purposes.
Removing Select ed Component s
You can remove any component ( s) from t he Select ed Component s list
by t he following st eps:
1. Highlight t he component ( s) you want t o delet e.
2. Click t he Remov e but t on, or press t he DELETE key.
For Library component s, UniSim Design removes t he component ( s)
from t he Select ed Component s list and places back in t he Component s
Available in t he Component Library list . Since Hypot het ical component s
are shar ed among Fluid Packages, t here is no act ual t ransfer bet ween
t he list s. ( i. e., The Hypo always appears in t he Available group, even
when it is list ed in t he select ed Component s list . )
Subst it ut ing Component s
When subst it ut ing component s, UniSim Design replaces t he component
t hroughout t he case ( i. e., all specificat ions for t he old component are
t ransferred t o t he new component ) . However, t he subst it ut ion funct ion
Fi gur e 1. 8
Refer t o Chapt er 3 -
Hy pot het i cal s for
det ailed informat ion on
Hypot het ical
component s.
You can only subst it ut e
one component at a
t ime. Even t hough
UniSim Design allows
you t o highlight mult iple
component s, t he
subst it ut ion only
involves t he first
highlight ed component .
1- 14
does not aut omat ically handle component s which are part of a
React ion.
You can subst it ut e a component in t he select ed Component List wit h
one in t he Component s Available in t he Component Library list by using
t he following procedure:
1. From t he select ed Component List , highlight t he component you
want t o remove.
2. I n t he Available Component list , highlight t he component t o be
subst it ut ed.
3. Click t he Subst i t ut e but t on.
4. The removed component is ret urned t o t he Available Component list
and t he subst it ut ed component is placed in t he Select ed Component
List .
Sort ing a Component List
When t here are component s in t he Select ed Component s group you can
use t he Sort List but t on t o rearrange t he component order.
Using t he view shown in Fi gur e 1.9, t he sort ing procedure is illust rat ed
below:
1. Click t he Sor t Li st but t on, and t he Move Component s view appears.
2. From t he Component ( s) t o Move group, select t he component you
want t o move. I n t his example, Met hane is select ed.
3. From t he I nsert Before group, highlight t he component before which
Met hane is t o be insert ed. I n t his case, Pr opane is highlight ed.
4. Click t he Mov e but t on t o complet e t he move. Met hane is insert ed
before Propane in t he component list , and Et hane is forced t o t he
t op of t he list , followed by Met hane, Propane, and n- But ane.
Fi gur e 1. 9
You can select and
highlight mult iple
component s for moving.
Component s 1- 15
1- 15
5. When you have complet ed t he sort ing, click t he Cl ose but t on t o
ret ur n t o t he Component s t ab.
Viewing Component s
Once a component is added t o t he Select ed Component s list , t he View
Component but t on becomes act ive. The View Component but t on
accesses t he Pure Component propert y view allowing you t o view and
edit propert ies of t he specified component .
The propert y views ar e different and are specific t o t he t ype of
component select ed. Pure library component s and hypot het ical
component s share t he first t ype of proper t y view. The difference
bet ween t he t wo is t hat you cannot direct ly modify t he propert ies in
t he pure component s Propert y View, whereas, in t he hypot het icals you
can. The Edi t Pr oper t i es feat ure allows you t o edit pure component
and solid propert ies.
The second pr opert y view is shared by pure component solids and
hypot het ical solids. Again you cannot direct ly modify t he pure
component solid propert ies, whereas, hypot het icals can be edit ed
direct ly.
The elect r olyt es proper t y view is t he same as t he edit propert ies
feat ure for library component s. Alt hough, t he elect rolyt e propert ies are
set by OLI syst ems and cannot be modified like t radit ional component s.
Each view consist s of five t abs. Throughout t he t abs t he informat ion is
displayed in red, blue and black. Values displayed in red are est imat ed
by UniSim Design. Values displayed in blue are user supplied. Black
values represent calculat ed values or informat ion t hat is pr ovided by
UniSim Design.
You can al so ex ami ne t he pr oper t y vi ew f or any component
i n t he Sel ect ed Component Li st by doubl e- cl i ck i ng on t he
component .
For more informat ion on
hypot het icals, refer t o
Chapt er 3 -
Hy pot het i cal s.
elect rolyt es, refer t o
Sect i on 1.2. 4 - Addi ng
El ect r ol y t e Component s.
1- 16
Pure Component Propert y View
I n t his example, Propane and Carbon are used by clicking t he View
Component but t on, which opens t he following t radit ional pure
component and Solid pure component propert y views, respect ively:
I D Tab
The I D t ab is t he first t ab in t he pr opert y view. The black values in t he
Component I dent ificat ion group represent informat ion t hat is provided
by UniSim Design. The User I D Tags are used t o ident ify your
component by a user specified t ag number. You can assign mult iple t ag
numbers t o each component .
Crit ical Tab & Props Tab
The Crit ical Tab displays Base and Crit ical Propert ies. The propert ies for
pure component s are supplied by UniSim Design and are r ead- only.
However, you can edit t hese propert ies using t he Edi t Pr oper t i es
but t on.
The Component Proper t y view for solid component s does not have
crit ical propert ies and t her efore does not requir e t he Crit ical t ab. An
alt ernat e t ab called t he Props t ab which displays default values for Solid
propert ies and Coal Analysis is included. These pr opert ies can also be
edit ed using t he Edit Proper t ies but t on.
Fi gur e 1. 10
You can also view a
component by right -
clicking on t he
component and
select ing Vi ew .
Component s 1- 17
1- 17
Point Tab
Addit ional Point propert ies are given by UniSim Design for t he
Thermodynamic and Physical Props and t he Propert y Package Molecular
Props. The pure component propert ies differ from t he solid propert ies.
The solid propert ies depend only on t he Heat of For mat ion and
Combust ion. These propert ies may be alt ered by select ing Point
propert ies in t he Edit Propert ies view.
TDep Tab
The Temperat ure Dependent Propert ies for pure component s are shown
in t his t ab. UniSim Design provides t he minimum t emperat ure,
maximum t emperat ure and coefficient s for each of t he t hree calculat ion
met hods.
The difference bet ween pur e component s and solid pure component s is
t hat solids do not part icipat e in VLE calculat ions. Their vapour pressure
informat ion is, by default , set t o zero. However, since solid component s
do affect Heat Balances, t he Specific Heat informat ion is used. The
propert ies may be edit ed by select ing t he Edit Propert ies but t on.
UserProp
The UserPr op t ab displays user specified proper t ies. User propert ies
must be specified on t he UserPropert y t ab in t he Simulat ion Basis
Manager view. Once a user propert y is specified t here, you can view
and edit UserPr op on t his component view.
PSD Tab
The PSD t ab displays t he part icle size dist ribut ion for solids. I t allows
t he user t o specify PSDs and calculat e various mean and modal
diamet ers for t he ent ered PSD.
Ent er i ng PSD dat a at t he Component or Fl ui d Pack age l ev el onl y
set s a def aul t f or y our si mul at i on model . Specific PSD informat ion
for feed st reams ( or in t he case of Dynamics, for reverse flowing
product st reams) should be set wit hin t he Simulat ion Environment .
You can set t he default PSD, however, if you would like t o specify a
fixed number of part icle sizes and diamet ers. This would t hen be your
default for feed st reams where you could t hen j ust override t he default
See Chapt er 7 - User
Pr oper t i es for more
informat ion.
1- 18
mass percent of each part icle size range.
I n Dynamic models, a simplified approach is t aken t o t he PSD
charact erizat ion when blending t wo st reams wit h a different number of
part icle sizes or wit h different diamet ers of par t icles. I n t his sit uat ion,
t he following rules are used:
1. I t will be assumed t hat t he weight percent bet ween t wo user
specified part icle sizes is evenly dist ribut ed. This means if a user
specifies, say, a minimum part icle size of 0. 001 mm and t he next
larger size as 0. 01 mm, and t hey have specified 50% of t he solid
component is wit hin t hat range, t hen we can infer ( or should I say
assume) t hat precisely 25% is wit hin ( 50% of 50%) t he range
0. 001 t o 0. 0055 mm. Similarly 50% * 0. 1111 = 5. 55% is wit hin
t he range 0. 001 t o 0. 002 mm, et c.
2. The mixing in t his sit uat ion will produce an out let PSD slat e which
preserves every part icle size ( and result ing part icle size range) of
every feed st ream. Users should not e t hat t his approach can
produce a very large number of part icles.
For Dynamics, t hen, t he Fit Type is irrelevant . I n t he implement at ion of
t his, t he St eady St at e mixing calculat ions are done by code which was
originally part of t he AEA Technology Solids Processing group ( SPS) . I n
Dynamics, a numerical mixing of t he feed dist ribut ion is done.
To edit a PSD, click t he Edit Propert ies but t on t o open t he Edit ing
Propert ies for Component view, select Type radio but t on in t he Sort By
group, and select Part icle Size Dist ribut ion from t he t r ee browser. The
opt ions available for edit t he PSD appears on t he right side of t he
Edit ing Proper t ies for Component view.
Fi gur e 1. 11
Special Dynamic
Modelling Not e.
Component s 1- 19
1- 19
A PSD can be specified in t hree ways:
The Basis but t on allows t he user t o select bet ween I n Size ( default ) ,
Under Size or Over Size. For t he I n Size opt ion t he percent ages are t he
mass ( or number) percent of t he solid wit hin t wo part icle sizes - t he
part icle size range. For Under Size, t his is t he cumulat ive percent of
t he solid component under t he specified part icle size ( but above t he
minimum size of course) . For Over Size, t his is t he cumulat ive percent
of t he solid component larger t han t he specified part icle size ( but less
t han t he maximum size of course) .
The input informat ion required for each I nput PSD are as follows:
The user has t he choice bet ween using t he User- Defined Discret e or
one of t he st at ist ical dist ribut ion met hods. The st at ist ical met hods ( Log
Probabilit y & Rosin- Rammler) may be preferr ed over t he discr et e
I nput PSD Gr oup Descr i pt i on
User - Def i ned
Di scr et e
Allows t he user t o ent er part icle diamet er vs
dist ribut ion values over t he range of t he dist ribut ion.
There are t wo t ypes of User- Defined Discret e, t he
Random and Geomet ric. To ent er t he Random
dist ribut ion, Select t he Edi t Di scr et e PSD but t on. The
ent ered dist ribut ion can be a Composit ion Basis wit h
mass percent or number percent dat a and can be
I nSize, cumulat ive Undersize or cumulat ive Oversize as
an I nput Basis. Once a discret ized PSD is ent ered, t he
user can have ot her t ypes of PSD fit t ed t o it . These fit s
are displayed in t he Fit Type group. The select ed fit can
be changed by regenerat ing t he fit at any t ime. To
ent er t he Geomet ric dist ribut ion, select t he Edit
Discret e PSD. Aft er user ent ered Minimum Part icle
Size, Maximum Part icle Size, Size Rat io and Number of
Sizes, Select t he Populat e Size but t on. The Part icle
Size values will be filled in aut omat ically. The user
needs only t o ent er t he percent age in each size range.
For Geomet ric dist ribut ion, t here is no fit t ing t o t he
ent ered dat a.
Log- pr obabi l i t y I s a t wo- paramet er st at ist ical represent at ion which
allows t he user t o specify t he mean and st andard
deviat ion of t he PSD.
Rosi n- Ramml er I s a t wo- paramet er st at ist ical represent at ion which
allows t he user t o specify t he Rosin- Rammler model
diamet er and spread paramet er of t he PSD.
I nput PSD Gr oup I nput I nf or mat i on Requi r ed
User - Def i ned
Di scr et e
The PSD requires basis, part icle densit y and number of
point s t o use in fit t ed PSDs. The dist ribut ion requires
part icle diamet ers ( including minimum diamet er) and
eit her I nSize, Undersize or Oversize dist ribut ion point s.
Log- pr obabi l i t y The PSD requires part icle densit y and number of point s
t o use in generat ing t he PSD. The dist ribut ion requires
mean diamet er and st andard deviat ion.
Rosi n- Ramml er The PSD requires part icle densit y and number of point s
t o use in generat ing t he PSD. The dist ribut ion requires
modal diamet er and spread paramet er.
1- 20
met hod if any of t he following occur s:
A number of part icle size measurement devices give t he
dist ribut ion as a st at ist ical fit .
Cert ain physical process t end t o give rise t o dist ribut ions t hat
are described well by a st at ist ical dist ribut ion. For example,
processes involving high shear ( e. g. cr ushing of coal,
at omizat ion of liquids in a t wo- fluid nozzle) t end t o give size
dist ribut ions t hat can be readily described by a Rosin- Rammler
dist ribut ion.
By using a st at ist ical dist ribut ion, it is easier t o ext end t he
dist ribut ion t o lower and higher size ranges. For many design
processes involving size dist ribut ions, it is t he values of t he
dist ribut ion at t hese ' t ails' t hat have most influence when t rying
t o opt imize t he design. Therefore, t he accuracy wit h which t hese
' t ails' can be described is import ant .
The Fit Type group for t he User- Defined Discr et e I nput allows t he user
t o fit a dist ribut ion t o t he ent ered discret e dat a. The fit t ing improves
t he accuracy of any calculat ions made by it .
I t increases t he number of discret e st eps over which a size
dist ribut ion can be described. The great er number of st eps
t aken increases t he accuracy of t he int erpolat ion.
I t provides more dat a at t he ext remes ( t ails) of t he dist ribut ion,
again improving accuracy.
The fit t ype used is based on which provides t he closest fit t o t he dat a.
The fit t ing alogorit hm displays a dialog wit h six fit s t o t he dat a. The
Aut oFit select s one fit for t he dat a aut omat ically, and t he NoFit does not
fit t he dat a. The St andard and Probabilit y fit t ypes are lagrangian
int erpolat ions on t he ent ered dat a, but one works on t he raw dat a while
one works on a probabilit y t ransformat ion of t he dat a. That is, t he
dist ribut ion values are t ransformed t o t he linear equivalent s used in
plot t ing against a probabilit y axis.
The ot her t wo fit s are a log- probabilit y and a Rosin- Rammler
dist ribut ion. For t hese t wo fit s, t he value of R
2
( t he fit coefficient ) is
given and t he closer t his is t o 1 t he bet t er t he fit . Ult imat ely, it is up t o
t he user t o choose t he best fit and is oft en based on t he visual
appearance of t he fit t ed dist ibut ions compared t o t he ent ered one. One
limit at ion t o PSD is t hat t he part icle diamet ers cannot be specified as
sieve mesh sizes.
I f you have already built a simulat ion model using Part icle Size
Dist ribut ion, or for t hat mat t er any different modified propert ies ( see
t he next sect ion under Edit Propert ies) , t hen you can easily reset your
model t o remove all aspect s of t he solids PSD modelling. Just use t he
"Reset Select ed Pr opert y for all users.. . " or "Reset All Propert ies for all
users. . . " but t ons as described in t he next sect ion. This is part icularly
import ant for dynamic models since t he holdups of t he dynamic unit
operat ions hold some of t he PSD modelling values and hence t hey need
t o be reset . Just removing t he PSD informat ion from feed st reams is
Component s 1- 21
1- 21
not enough t o complet ely remove all remnant s of PSD modelling.
Once you have used t he but t ons " Reset Select ed Propert y for all
user s. . . " or "Reset All Pr opert ies for all users. . . " you may st ill see t hese
propert ies in t he st reams and simulat ion BUT t hese propert ies and
values will now only be from t he Fluid Package or Component level
default . The simulat ion will not be doing any calculat ions based upon
t hese values but inst ead every st r eam will j ust show t he same values
( i. e. t he Fluid Package or Component default s) . To remove t hese
remnant s, j ust use t he but t ons "Reset Select ed Proper t y t o library
default " or " Reset All Propert ies t o library default " .
Coal Tab
The Coal t ab displays t he coal propert ies informat ion of hypo solid
component . I t allows user t o specify a hypo solid component as a coal
component , and est imat e it s pr opert ies.
To define a hypo solid component as coal, t he st ep one is t o check on
t he I s Coal ? check box. Then user has t wo choices for st ep t wo: use
default coal proper t ies or specify coal propert ies. The default coal
propert ies are designed for users t o reduce effort of defining a coal
component where default coal propert ies are adequat e. By clicking
Def aul t Coal but t on, coal propert ies will be set t o default value and
ready t o use. I f user would like t o define your own coal pr opert ies, t he
input of Coal Element Mass Fract ion, Coal I ndust ry Analysis Mass
Fract ion and Ash propert y are r equired.
There ar e defining and est imat ing Coal Propert ies eit her by:
Clicking t he Edi t Coal but t on on t he Coal Tab
Fi gur e 1. 12
1- 22
or
Clicking t he Edi t Pr oper t i es but t on t o open t he Edit ing
Propert ies for Component view, select Type radio but t on in t he
Sort By group, and select Coal Pr oper t i es from t he t ree
browser. Expand t he group and select Coal Propert y. The opt ions
available for edit ing t he Coal Propert y appear on t he right side of
t he Edit ing Proper t ies for Component view.
The following are descript ions for input and est imat ed coal pr opert ies.
Fi gur e 1. 13
Coal Pr oper t y Desscr i pt i on
Coal El ement Mass
Fr act i on
( also called coal
ult imat e analysis)
I t is user provided mass fact ion of element carbon,
hydrogen, oxygen, nit rogen, sulfur and chlorine, on dried
and ash free base of coal sample from ult imat e analysis.
Sum of input s of Coal Element Mass Fract ion must be 1.
You can click Nor mal i ze I nput s but t on t o normalize t he
input dat a.
Coal I ndust r y
Anal y si s
( also called coal
proximat e analysis)
I t is user provide mass fract ion of fixed carbon, volat iles,
moist ure and ash on a received base of coal sample. Sum
of input s of Coal I ndust ry Analysis dat a must be 1. You
can click Nor mal i ze I nput s but t on t o normalize t he input
dat a.
Char Pr oper t y The Char propert ies dat a are ret rieved from UniSim
Design t radit ional library component Graphit e carbon.

Char Mw is t he carbon Molecular weight
Char HF is t he carbon Heat of format ion
Al pha, Bet a, Gama and Del t a are t he coeffs of
carbon heat capacit y ( kJ/ kgmol) vs t emperat ure ( K)
correlat ion:
Cp = Alpha + Bet a * T + Gama * T^ 2 + Delt a * T^ 3.
Component s 1- 23
1- 23
Ash Pr oper t y User input is required for Ash propert ies dat a.
Ash Mw is t he ash Molecular weight
Ash HF is t he carbon Heat of format ion
Al pha, Bet a, Gama and Del t a are t he coeffs of
carbon heat capacit y ( kJ/ kgmol) vs t emperat ure ( K)
correlat ion:
Cp = Alpha + Bet a * T + Gama * T^ 2 + Delt a * T^ 3.
1- 24
By clicking Est i mat e Pr oper t i es but t on, coal analysis will est imat e t he
rest of coal propert ies including composit ion of volat iles, High Heat
Value, Low Heat Value, coal average molecular weight and heat of
Est i mat ed Coal
Pr oper t y
For mul a is t he coal formula
Mw is t he coal molecular weight
HF is t he coal Heat of format ion
HHV is t he coal high heat value
=
where:
fixed carbon High heat value = 32815. 83333
kJ/ kg;
fixed carbon mass fract ion from I ndust rial
Analysis;
volat ile mass fract ion from I ndust rial Analysis;
H2 high heat value = 120907 kJ/ kg;
est imat ed volat ile H2 mass fract ion;
CO high heat value = 10114.28571 kJ/ kg;
est imat ed volat ile CO mass fract ion;
C6H6 high heat value = 40655. 88462
kJ/ kg;
est imat ed volat ile C6H6 mass fract ion;
LHV is t he coal low heat value
where:
fixed carbon low heat value = 32815. 83333
kJ/ kg;
fixed carbon mass fract ion from I ndust rial
Analysis;
volat ile mass fract ion from I ndust rial
Analysis;
H2 low heat value = 96607.18714 kJ/ kg;
est imat ed volat ile H2 mass fract ion;
CO low heat value = 10114.28571 kJ/ kg;
est imat ed volat ile CO mass fract ion;
C6H6 low heat value = 38398. 83372 kJ/
kg;
est imat ed volat ile C6H6 mass fract ion;
a, b, c, d and e are t he coeffs of t he coal heat
capacit y ( kJ/ kgmol) vs t emperat ure ( K) correlat ion:

Cp = a + b * T + c * T^2 + d * T^3 + e * T^4.
C
HHV
C
mf
- H2
HHV
H2
mf
- CO
HHV
CO
mf
- C6H6
HHV
C6H6
mf
- + + ( ) C
mf
V
mf
+ ( ) +
C
HHV
C
mf
V
mf
H2
HHV
H2
mf
CO
HHV
CO
mf
C6H6
HHV
C6H6
mf
C
LHV
C
mf
H2
LHV
H2
mf
CO
LHV
CO
mf
C6H6
LHV
C6H6
mf
- + - + - ( ) + - C
mf
V
mf
+ ( )
C
LHV
C
mf
V
mf
H2
LHV
H2
mf
CO
LHV
CO
mf
C6H6
LHV
C6H6
mf
Component s 1- 25
1- 25
format ion, as well as cor relat ion coefficient s of heat capacit y Cp versus
t emperat ure T based on t he input dat a.
The coal propert ies as defined in Basis Environment would be your
default coal pr opert ies for feed st reams where you could t hen j ust over-
ride t he default coal propert ies by t he use of Propert y Edit or at t he
st ream level. When blending t wo st reams wit h different coal propert ies
for t he same coal compound, it will be assumed t hat t he weight percent
bet ween t wo user specified coal propert ies is evenly dist ribut ed. A
numerical mixing of t he feed dist ribut ion is done.
Edit Propert ies
The Edit Propert ies but t on allows t he user t he flexibilit y of viewing and
modifying propert ies for t radit ional and hypot het ical component s.
Elect r olyt e component propert ies are specified by OLI Syst ems which
may only be viewed. The Edit Propert ies View can be accessed on t hree
different levels and are shown below:
Component l ev el . Double- click on any component or right - click
and select View. Click t he Edit Propert ies but t on.
Fl ui d Pack age l ev el . Click t he Edit Propert ies but t on on t he
Fluid Package view.
St r eam l ev el . Select a mat erial st r eam and click t he Edit
Propert ies but t on on t he Composit ion page.
The Component level Edit Propert ies view is shown below for met hane.
Fi gur e 1. 14
1- 26
The propert ies can be sort ed using t he Sort By group on any level.
The Edit Propert ies feat ure is flexible in t hat it allows you t o edit
propert ies on t he component , fluid package, or st ream levels. The
component level is t he highest and allows you t o edit propert ies
t hroughout your case. Any changes at t his level correspond t o a global
change t o all fluid packages using t he part icular component . The init ial
value st ored at t his level for any given component is considered t he
' default ' pr opert y value.
At t he component level, t he reset opt ions are described below.
The second level is t he fluid package level which allows you t o edit
propert ies specific t o a fluid package. This allows t he flexibilit y of
having different pr opert y values for different fluid packages t hroughout
t he case. Any changes at t his level will affect all flowsheet obj ect s using
t he Fluid Pkg.
Sor t By Descr i pt i on
Pr oper t y Name Sort by Propert y Name.
Gr oup Sort by Groups. This includes Thermo, Prop Pkg,
Physical, Cold, Solid, et c.
Ty pe Sort by propert y t ypes such as Point , Curve,
Dist ribut e, PSD, Coal Propert y and Hydrat e et c.
Modi f y St at us Sort by Modified and Not Modified in t he specific
Component , Fluid Pkg, or St ream.
Component Level Reset Descr i pt i on
Reset sel ect ed pr oper t y
t o l i br ar y def aul t
Reset s t he select ed propert y t o t he library or
original default value for t his component . This
but t on is act ive only if a component is
modified on t he component level.
Reset al l pr oper t i es t o
l i br ar y def aul t
Reset s all propert ies t o library or original
default values for t his component . This but t on
is act ive only if a component is modified on
t he component level.
Reset sel ect ed pr oper t y
f or al l user s of t hi s
component
Clears local changes t o t he select ed propert y
for all users of t his component . This will
overwrit e t he changes in t he Fluid Pkg and
st ream levels by t he current component
value.
Reset al l pr oper t i es f or
al l user s of t hi s
component
Clears local changes t o all propert ies for all
users of t his component . This will overwrit e
t he changes in t he Fluid Pkg and st ream levels
corresponding t o t his component by t he
current values of t he component .
Component s 1- 27
1- 27
The reset opt ions for t he fluid pkg level are described below:
The st ream level allows you t o edit propert ies specific t o feed st reams
of t he case. Changes made at t his level enable one t o modify a
part icular component ' s pr opert y for a part icular st ream. This allows t he
flexibilit y of propert ies t o dynamically change across t he flowsheet .
The reset opt ions are list ed below and are act ive if you modify a
propert y value at t he st ream level.
The propert ies for t he st ream are accessible from t he st ream level
edit or. However, only t he feed st r eam propert ies are modifiable.
Keep in mind t hat any propert y vect or changes at t he St ream level
supercede changes at t he fluid package level. For example, if a st ream
is t rying t o access a part icular component ' s ' Point ' pr opert y value and
t he propert y vect or is cont ained in t he st ream' s local propert y slat e, t he
local value is used. I f t he propert y vect or does not exist locally, t hen it
calls up t o t he fluid package' s propert y slat e for t he part icular propert y
vect or and uses t his value if it exist s. I f t he propert y vect or does not
exist at t he fluid package level, t hen t he init ial Component level value is
used.
Fl ui d Pk g Lev el Reset Descr i pt i on
Reset sel ect ed pr op
vect or t o
component s v al ues
Clears t he select ed propert y vect or wit hin t his fluid
package and reset s it t o t he component level
value.
Reset al l pr ops t o
component s v al ues
Clears all changed propert y vect ors wit hin t his
fluid package and reset s t hem t o t he component
level values.
Reset sel ect ed
pr oper t y f or al l user s
of t hi s Fl ui d Pk g
Clears local changes t o select ed propert y vect or
for all users of t his fluid package. This will
overwrit e t he st ream level change wit h t he current
vect or in t he fluid package.
Reset al l pr oper t i es
f or al l user s of t hi s
Fl ui d Pk g
Clears local changes t o all propert ies for all users
of t his fluid package. This will overwrit e all of t he
st ream level changes wit h t he current vect ors in
t he fluid package.
St r eam Lev el Reset Descr i pt i on
Reset sel ect ed pr op
vect or t o FP v al ues
Clears select ed propert y vect or and reset it t o t he
fluid package level value for t his st ream.
Reset al l pr ops t o FP
val ues
Clears all changed propert y vect ors and reset
t hem t o t he fluid package values for t his st ream.
1- 28
1. 2. 4 Adding Elect rolyt e
Component s
Elect rolyt e Component s can be added t o t he component list in t he
Component List view. I n t he Add Component group of t he Select ed t ab,
select t he Elect rolyt e page locat ed as t he subgroup of t he Component s
library configurat ion.
The view is filled wit h informat ion on elect rolyt es as shown below.
The met hods for adding, subst it ut ing, removing, and sort ing
component s are common for all component s on t he select ed t ab. The
filt ering opt ions for Elect rolyt es are described in t he following t able:
You can select AE dat abank for aqueous- based chemical syst em by
clicking t he AE radio but t on or choose MSE radio but t on for mixed
solvent chemical syst em. The AE or MSE dat abank is support ed by
different library component dat abases and chemist ry models in t he
engine.
For AE dat abank select ion, addit ional elect rolyt e component dat abases
t o simulat e special aqueous- based chemical syst ems are provided.
UniSim Design support s t wo special dat abases: GEOCHEM, LOWTEMP,
Fi gur e 1. 15
Fi l t er Descr i pt i on
Mat ch This input cell allows t ype- mat ching of t he component
simulat ion name, full name / synonym, or formula based on
t he radio but t on select ed.
Refer t o Fi l t er i ng t he
Component Li st f or
Tr adi t i onal
Component s for
addit ional informat ion on
using t he Mat ch field t o
filt er t he component list
for t radit ional
component s.
Refer t o t he following
sect ions in t he Uni Si m
Desi gn OLI I nt er f ace
Ref er ence Gui de for
more informat ion on t he
OLI dat abases:
Sect i on 1.8. 1 - Ful l
Dat abase
Sect i on 1. 8. 2 -
Li mi t ed Dat abase
Sect i on 1. 8. 3 -
Speci al Dat abases
Sect i on 1. 8. 4 -
Pr i vat e User
Dat abases - OLI
Dat a Ser vi ce
Component s 1- 29
1- 29
and REDOX opt ion ( refer t o Sect i on 1. 8. 3 - Speci al Dat abases from
t he Uni Si m Desi gn OLI I nt er f ace Ref er ence Gui de for more
informat ion) . The REDOX opt ion support s bot h AE and MSE dat abank
opt ions.
You can access t hose special dat abases by clicking on t he Addit ional
Dat abase but t on, and select t he desired special dat abases from t he
Special Dat abank gr oup in t he OLI _Elect rolyt e Addit ional Dat abase
view. The use of GEOCHEM, LOWTEMP, and REDOX dat abases depends
on your licence agreement wit h OLI Syst em I nc. which can provide a
Full access licence or a Limit ed licence t o meet your needs. You can also
supply your own OLI privat e dat abank t o suit t he need of your
simulat ion case.
To get a comprehensive list of t he Full, and GEOCHEM dat abase
component s, refer t o:
Appendi x A. 1 - Li st of Uni Si m Desi gn OLI I nt er f ace Ful l
Dat abase, of t he Uni Si m Desi gn OLI I nt er f ace Ref er ence
Gui de.
Appendi x B. 1 - Li st of Uni Si m Desi gn OLI I nt er f ace
GEOCHEM Dat abase, of t he Uni Si m Desi gn OLI I nt er f ace
Ref er ence Gui de.
Appendi x C. 1 - Li st of Uni Si m Desi gn OLI I nt er f ace Ful l
Dat abase, of t he Uni Si m Desi gn OLI I nt er f ace Ref er ence
Gui de.
1. 2. 5 Adding Hypot het ical
Component s
Hypot het icals can be added t o a component list t hrough t he
Component s List View. I n t he Add Component group of t he Select ed
t ab, select t he Hypot het ical Component s, Tradit ional or Elect rolyt e page
from t he t r ee configurat ion list . The Component s List View is filled wit h
Refer t o Sect i on 3. 5 -
Hy pot het i cal
Component Pr oper t y
Vi ew for det ails on t he
various Component
propert y view t abs.
1- 30
informat ion appropriat e t o t he addit ion of Hypot het ical component s.
Some of t he feat ures from t he Select ed t ab are common t o bot h t he
select ion of Hypot het icals and Library component s. I t ems specific t o
Hypot het icals are described in t he following t able:
Fi gur e 1. 16
Add Gr oup At t he select ion of Tradit ional subgroup of Hypo
Component , adds all t he Hypot het ical component s in
t he select ed Hypo Group t o t he current component list .
Add Hypo At t he select ion of Tradit ional subgroup of Hypo
Component , adds t he current ly select ed Hypot het ical
t o t he current component list .
Add E Gr oup At t he select ion of Elect rolyt e subgroup of Hypo
Component , adds all t he Hypot het ical component s in
t he select ed Hypo Group t o t he current Elect rolyt e
component list .
Add E Hy po At t he select ion of Elect rolyt e subgroup of Hypo
Component , adds t he current ly select ed Hypot het ical
t o t he current component list .
Av ai l abl e Hy po
Gr oups
Displays all t he Hypo Groups available t o t he current
component list .
Av ai l abl e Hy po
Component s
Displays all t he Hypot het ical component s cont ained in
t he current ly select ed Hypo Group.
Hy po Manager Accesses t he Hypot het icals t ab of t he Simulat ion Basis
Manager, from which you can creat e, view, or edit
Hypot het icals.
Qui ck Cr eat e a
Hy po Component
A short - cut for creat ing a regular Hypot het ical
component and adds it t o t he current ly select ed Hypo
Group and opens it s propert y view.
Qui ck Cr eat e a
Sol i d component
A short - cut for creat ing a solid Hypot het ical component
and adds it t o t he current ly select ed Hypo Group and
opens it s propert y view.
Hy pot het i cal s for more
det ailed informat ion t o
Add and modify
Hypot het ical component s.
Component s 1- 31
1- 31
1. 2. 6 Adding Component s from
Exist ing Component List s
Component s can be added from ot her component list s by using t he
Ot her Component List opt ion. I n t he Add Component group, select t he
Ot her Component s List . The Component s t ab is redrawn wit h
informat ion appropriat e t o accessing component s from alt ernat e
component list s.
The Exist ing Component s group displays a list of all available
component list s loaded int o t he current case. Highlight ing a component
list name displays it s associat ed gr oup of component s in t he
Component s in Select ed Component List .
To t ransfer a component from an exist ing component list , simply
highlight t he component name in t he list and click t he Add but t on. The
highlight ed component is added t o t he Select ed Component s list .
Add E Gr oup and Add E Hy po But t ons ar e l i mi t ed f or addi ng a
hypot het i cal component i nt o an El ect r ol y t e Component l i st
onl y .
The name of t he Hy po component , as soon as bei ng added
i nt o t he El ect r ol y t e Component l i st , w i l l be modi f i ed by
r epl aci ng t he * at t he end w i t h E and t he I D number w i l l be
bumped up by 50000.
Fi gur e 1. 17
Pet r ol eum Fr act i on in
t he OLI I nt erface
Reference Guide for more
informat ion on t he
OLI _Elect royle fluid
package .
1- 32
Fl ui d Pack age 2- 1
2- 1
2 Fluid Package
2.1 I nt r oduct i on ............. ........................................................... .......... 2
2.2 Fl ui d Pack ages Tab ... ........................................................... .......... 2
2.3 Addi ng a Fl ui d Pack age - Ex ampl e ....................................... .......... 4
2.4 Uni Si m Desi gn Fl ui d Pack age Pr oper t y Vi ew ........................ .......... 6
2.4.1 Set Up Tab . .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
2.4.2 Paramet ers Tab.. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 22
2.4.3 Binary Coefficient s Tab. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 44
2.4.4 St abilit y Test Tab.. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 54
2.4.5 Phase Order Tab .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 58
2.4.6 React ions Tab . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 62
2.4.7 Tabular Tab .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 63
2.4.8 Not es Tab .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 83
2.5 Uni Si m Ther mo Pr oper t y Vi ew ............................................. .........84
2.5.1 Set Up Tab . .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 85
2.5.2 Paramet ers Tab.. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 96
2.5.3 Binary Coefficient s Tab. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 97
2.5.4 St abilit y Test Tab.. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. 100
2.5.5 React ions Tab . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. 104
2.5.6 Not es Tab .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. 104
2.6 Ref er ences................ ........................................................... ....... 104
2- 2
I n UniSim Design, all necessary informat ion pert aining t o pure
component flash and physical propert y calculat ions is cont ained wit hin
t he Fluid Package. This approach allows you t o define all t he required
informat ion inside a single ent it y. There are four key advant ages t o t his
approach and are list ed below:
All associat ed informat ion is defined in a single locat ion, allowing
for easy creat ion and modificat ion of t he informat ion.
Fluid Packages can be export ed and import ed as complet ely
defined packages for use in any simulat ion.
Fluid Packages can be cloned, which simplifies t he t ask of
making small changes t o a complex Fluid Package.
Mult iple Fluid Packages can be used in t he same simulat ion;
however, t hey are all defined inside t he common Simulat ion
Basis Manager.
I n t his chapt er, all informat ion concerning t he fluid package are
covered. This includes t he basic procedure for creat ing a fluid package
by using bot h t radit ional UniSim Design and UniSim Thermo
t hermodynamics. Finally, informat ion on t he Fluid Package proper t y
view is provided for each of t he following t abs:
Set Up
Paramet ers
Binary Coefficient s
St abilit y Test
Phase Order
React ions ( Rxns)
Tabular
Not es
I t should be not ed t hat individual component s are not added wit hin t he
Fluid Package Manager. I nst ead, component select ion is handled
independent ly in t he Basis Manager t hrough t he Component s t ab. The
Component s Manager provides a general locat ion where set s of
chemical component s being modeled may be ret r ieved and
manipulat ed.
2. 2 Fluid Packages Tab
The next t ab of t he Simulat ion Basis Manager view is t he Fluid Packages
( Fluid Pkgs) t ab. When you cr eat e a New Case, UniSim Design displays
Component s for furt her
det ails on t he
Component s Manager.
You must define at least
one fluid package prior t o
ent ering t he Simulat ion
Environment .
2- 3
t he Fluid Pkgs t ab, as shown below:
I n t he Current Fluid Packages group, t here are but t ons t hat allow you
t o organize all Fluid Packages for t he current case.
The following t able list s and describes each but t on:
The Flowsheet - Fluid Pkg Associat ions group list s each Flowsheet in t he
current simulat ion along wit h it s associat ed Fluid Package. You can
change t he associat ions bet ween Flowsheet s and which Fluid Pkg To
Use in t his locat ion. You can also specify a default fluid package by
select ing a package in t he Default Fluid Pkg dr opdown list . UniSim
Fi gur e 2. 1
When a New Case i s cr eat ed, onl y t he Add and I mpor t
but t ons ar e avai l abl e.
Vi ew This is only act ive when a fluid package exist s in t he
case. I t allows you access t he propert y view for t he
select ed fluid package.
Add Allows you t o inst all a new fluid package int o t he case.
Del et e Allows you t o delet e a fluid package from t he case. When
you delet e a fluid package, UniSim Design displays a
warning, and asks you t o verify t hat you want t o delet e
t he package. You must have at least one fluid package
for your case at all t imes.
Copy Makes a copy of t he select ed fluid package. Everyt hing is
ident ical in t his copied version, except t he name. This is a
useful t ool for modifying fluid packages.
I mpor t Allows you t o import a pre- defined fluid package from
disk. Fluid packages have t he file ext ension * . f pk .
Ex por t Allows you t o export t he select ed fluid package ( * . f pk )
t o disk. The export ed fluid package can be ret rieved int o
anot her case, by using it s I mport funct ion.
Uni Si m Desi gn Fl ui d
Pack age Pr oper t y
Vi ew for det ails on what
informat ion you can edit
by clicking t he View
but t on.
For det ails concerning
t he import ing and
export ing funct ionalit y,
refer t o Sect i on 7. 24. 7
- Ex por t i ng/
I mpor t i ng Wor k book
Tabs in t he Uni Si m
Desi gn User Gui de.
2- 4 Addi ng a Fl ui d Pack age - Ex ampl e
2- 4
Design aut omat ically assigns t he Default Fluid Package t o each unit
operat ion, SubFlowsheet or columns using t he default fluid package in
t he simulat ion.
Select ing a alt er nat ive fluid package from t he Basis Manager view
allows you t o t ransit ion or swit ch bet ween fluid pkgs anywhere in t he
flowsheet wit h t he addit ion of t he st ream cut t er obj ect .
The Fluid Pkg for New Sub- FlowSheet s group allows you t o select t he
default fluid package t hat is associat ed t o a subflowsheet , when t he
subflowsheet is creat ed.
Use Def aul t Fl ui d Pk g radio but t on associat es t he default fluid
package of t he ent ire simulat ion case t o t he subflowsheet .
Use Par ent s Fl ui d Pk g radio but t on associat es t he default
fluid package of t he parent flowsheet t o t he subflowsheet .
2. 3 Adding a Fluid Package -
Example
When you click t he Add but t on from t he Simulat ion Basis Manager view,
UniSim Design opens t he Fluid Package pr opert y view t o t he Set Up t ab.
The Fluid Package view is based on t he t radit ional UniSim Design
Thermodynamics.
Changi ng t he def aul t pack age onl y changes t hose f l ui d pk gs
t hat ar e cur r ent l y set t o use t he def aul t f l ui d pack age. That
i s, any oper at i on or st r eam w hi ch i s not set t o t he def aul t
f l ui d pack age i s not modi f i ed.
Fi gur e 2. 2
Logi cal Oper at i ons in t he
Uni Si m Desi gn
Oper at i ons Gui de for
det ailed informat ion on t he
st ream cut t er obj ect and
fluid package t ransit ioning.
You can check t he UniSim Thermo checkbox t o access t he UniSim
Thermo opt ion in UniSim Design.
2- 5
The or der of t he t abs in t he Fluid Package propert y view are t ied t o t he
sequence of defining a Fluid Package using UniSim Design
t hermodynamics.
On t he Set Up t ab, select a Propert y Package for t he case from
t he Propert y Package Select ion group. You can filt er t he list of
Propert y Packages by select ing a radio but t on in t he Propert y
Package Filt er group. You must also select a Component List for
t he case from t he Component List Select ion group. Component
List s are built in t he Simulat ion Basis Manager and may cont ain
library, hypot het ical, and elect rolyt e component s.
Depending on t he Propert y Package select ed, you may need t o
specify addit ional informat ion, such as t he Ent halpy and Vapour
Model, Poynt ing Correct ion fact or, et c.
Depending on t he Propert y Package select ed you may need t o
supply addit ional informat ion based on t he select ed
component s. This is done on t he Paramet ers t ab.
I f necessary, specify t he binary coefficient s on t he Binar y Coeffs
t ab. As an alt ernat ive t o supplying binaries, you may want t o
have est imat es made for t he select ed component s.
I f necessary, inst ruct UniSim Design how t o perform Phase
St abilit y t est s as part of t he flash calculat ions on t he St ab Test
t ab.
Define any r eact ions and react ion set s for t he fluid package or
access t he React ion Manager on t he Rxns t ab.
On t he Tabular t ab, you can access t he Tabular Package for t he
equat ion based r epresent at ion of t arget ed proper t ies.
The final t ab on t he Fluid Package propert y view is t he Not es
t ab, where you can supply descript ive not es for t he new Fluid
Package.
I f you click t he UniSim Thermo checkbox in t he Advanced
Thermodynamics group, UniSim Design opens t he Fluid package
propert y view t o t he Set Up t ab. The Fluid Package view is based on t he
UniSim Thermodynamics framework.
The order of t he t abs in t he Fluid Package propert y view are similar t o
t he t radit ional UniSim Design Thermodynamics as above except for t he
Fi gur e 2. 3
A complet e descript ion of
each page of t he Fluid
Package propert y view is
given in Sect i on 2. 4 -
Pack age Pr oper t y
Vi ew .
For furt her det ails relat ing
t o Component List s and
component select ion,
refer t o Chapt er 1 -
Component s.
React i ons for
React ion Manager.
2- 6 Uni Si m Desi gn Fl ui d Pack age
2- 6
following:
On t he Set Up t ab, select a model case from t he Model Select ion
group for t he vapor and liquid phase.
Depending on t he model select ed, you may specify addit ional
informat ion. For example, in t he Model Opt ions group select t he
calculat ion met hods for Ent halpy and Ent ropy, Cp, et c., using t he
drop- down list .
Depending on t he Model select ed, you may need t o supply
addit ional informat ion based on t he select ed component s. This is
done on t he Paramet ers t ab.
I f necessary, specify t he binary coefficient s on t he Binary Coeff
t ab. As an alt ernat ive t o supplying binaries, you may want t o
have est imat es made for t he select ed component s.
I f necessary, inst ruct UniSim Design- UniSim Thermo how t o
perform Phase St abilit y t est s as part of t he flash calculat ions on
t he St ab Test t ab.
2. 4 UniSim Design Fluid
Package Propert y View
The Fluid Package propert y view consist s of eight t abs and is based on
t he t radit ional UniSim Design t hermodynamics. Among t hese t abs is all
t he informat ion pert aining t o t he part icular Fluid Package.
Fi gur e 2. 4
Removes t he Fluid
Package from t he
case. You must
confirm t hat you want
t o delet e t he Fluid
Package
You can input a name
for t he Fluid Package
in t his field.
The select ed base
Propert y Package t ype is
shown in t his st at us bar.
Click t his but t on t o
edit propert ies at t he
fluid package level.
2- 7
2. 4. 1 Set Up Tab
The Set Up t ab is t he first t ab of t he Fluid Package pr opert y view.
When you creat e a new Fluid Package, t he Fluid Package view appears
as shown in t he above above.
The Set Up t ab cont ains t he Propert y Package Select ion, Component
List Select ion, Propert y Package Filt er and Thermodynamics groups.
Once a Propert y Package is select ed, addit ional informat ion and opt ions
may be displayed t o t he right of t he Propert y Package Select ion group.
This is shown in Fi gur e 2.4 wit h t he EOS Ent halpy Met hod
Specificat ion group for t he Peng- Robinson pr opert y package. The
informat ion t hat is displayed is dependent on t he select ed Pr opert y
Package.
The following sect ions provide an overview of t he various Propert y
Packages, as well as det ails on t he various groups t hat appear on t he
Set Up t ab.
Propert y Package Select ion
I n t he Propert y Package Select ion group, you have access t o t he list of
all t he Propert y Package/ Proper t y Met hods available in UniSim Design
and t o t he Propert y Package Filt er group.
Fi gur e 2. 5
Uni Si m Ther mo
Pr oper t y Vi ew for more
informat ion on Advanced
Thermodynamics group.
Addit ional informat ion are displayed
in t his space depending on t he
Propert y Package select ion.
Select a Component List here. I t is not recommended
t o use t he Mast er Component List .
Select a propert y package
for t he fluid package using
t he propert y package filt er.
For more det ailed
informat ion about t he
propert y packages
available in UniSim
Design, refer t o
Appendi x A - Pr oper t y
Met hods &
Cal cul at i ons.
2- 8
The Propert y Package Filt er allows you t o filt er t he list of available
propert y met hods, based on t he following crit eria:
Equat ions of St at e ( EOS)
For oil, gas and pet rochemical applicat ions, t he Peng- Robinson Equat ion
of St at e is generally t he recommended propert y package. The
enhancement s t o t his equat ion of st at e enable it t o be accurat e for a
variet y of syst ems over a wide range of condit ions. I t rigorously solves
most single phase, t wo phase and t hree- phase syst ems wit h a high
degree of efficiency and reliabilit y.
All equat ion of st at e met hods and t heir specific applicat ions are
described below:
Fi l t er Descr i pt i on
Al l Ty pes All t he Propert y Packages appear in t he list .
EOSs Only Equat ions of St at e appear in t he list .
Act i v i t y Model s Only Liquid Act ivit y Models appear in t he list .
Chao Seader
Model s
Only Chao Seader based Semi Empirical met hods
are displayed.
Vapour Pr essur e
Model s
Vapour pressure K- value models are shown in t he
list .
El ect r ol y t e Model s I deal Elect rolyt e Package and Urea Elect rolyt e
Package are displayed.
Mi scel l aneous Models t hat do not fit int o any of t he above 4
cat egories ( i. e., excluding Al l ) are displayed.
EOS Descr i pt i on
BWRS This equat ion of st at e can be used for hydrocarbon
syst ems.
GCEOS This model allows you t o define and implement your own
generalized cubic equat ion of st at e including mixing rules
and volume t ranslat ion.
Gl ycol Pk g Glycol propert y package cont ains t he TST ( Twu- Sim-
Tassone) equat ion of st at e t o det ermine t he phase
behaviour more accurat ely and consist ent ly for t he TEG-
wat er mixt ure.
Kabadi Danner This model is a modificat ion of t he original SRK equat ion
of st at e, enhanced t o improve t he vapour- liquid- liquid
equilibria calculat ions for wat er- hydrocarbon syst ems,
part icularly in dilut e regions.
Lee- Kesl er
Pl ock er
This model is t he most accurat e general met hod for non-
polar subst ances and mixt ures.
MBWR This is a modified version of t he original Benedict / Webb/
Rubin equat ion. This 32- t erm equat ion of st at e model is
applicable for only a specific set of component s and
operat ing condit ions.
t he package see
Appendi x D - Gl y col
Pr oper t y Pack age.
2- 9
Act ivit y Models
Alt hough Equat ion of St at e models have proven t o be very reliable in
predict ing t he propert ies of most hydrocarbon based fluids over a wide
range of operat ing condit ions, t heir applicat ion is limit ed t o primarily
non- polar or slight ly polar component s. Highly non- ideal syst ems are
best modeled using Act ivit y Models.
The following Act ivit y Model Pr opert y Packages are available:
Peng- Robi nson This model is ideal for VLE calculat ions as well as
calculat ing liquid densit ies for hydrocarbon syst ems.
Several enhancement s t o t he original PR model were
made t o ext end it s range of applicabilit y and t o improve
it s predict ions for some non- ideal syst ems. However, in
sit uat ions where highly non- ideal syst ems are
encount ered, t he use of Act ivit y Models is recommended.
PRSV This is a t wo- fold modificat ion of t he PR equat ion of st at e
t hat ext ends t he applicat ion of t he original PR met hod for
moderat ely non- ideal syst ems.
PR- Tw u
SRK- Tw u
Tw u- Si m-
Tassone ( TST)
The maj or advant age t hese t hree equat ions of st at e over
ot her cubic equat ions of st at e is t hat t hese t hree include
an exponent ial t erm which provides smoot h t ransit ion
t hrough crit ical condit ions. Select from t hese t hree when
supercrit ical compounds are ant icipat ed.
SRK I n many cases it provides comparable result s t o PR, but
it s range of applicat ion is significant ly more limit ed. This
met hod is not as reliable for non- ideal syst ems.
Sour PR Combines t he PR equat ion of st at e and Wilson' s API - Sour
Model for handling sour wat er syst ems.
Sour SRK Combines t he Soave Redlich Kwong and Wilson' s API -
Sour Model.
Zudk ev i t ch
Jof f ee
Modificat ion of t he Redlich Kwong equat ion of st at e. This
model has been enhanced for bet t er predict ion of
vapour- liquid equilibria for hydrocarbon syst ems, and
syst ems cont aining Hydrogen.
Act i v i t y Model Descr i pt i on
Chi en Nul l Provides a consist ent framework for applying exist ing
Act ivit y Models on a binary by binary basis. I t allows you
t o select t he best Act ivit y Model for each pair in your
case.
Ex t ended NRTL This variat ion of t he NRTL model allows you t o input
values for t he A
ij
, B
ij
, C
ij
, Alp1
ij
and Alp2
ij
paramet ers
used in defining t he component act ivit y coefficient s.
Apply t his model t o syst ems:
wit h a wide boiling point range bet ween
component s.
where you require simult aneous solut ion of VLE and
LLE, and t here exist s a wide boiling point range or
concent rat ion range bet ween component s.
EOS Descr i pt i on
Refer t o Sect i on 2.4. 2 -
Par amet er s Tab for
more informat ion on
Sect i on - Modi f y H2 Tc
and Pc Opt i on and
Sect i on - I ndex ed
Vi scosi t y Opt i on.
2- 10
Chao Seader & Grayson St reed Models
The Chao Seader and Grayson St reed met hods are older, semi-
empirical met hods. The Grayson St reed correlat ion is an ext ension of
t he Chao Seader met hod wit h special emphasis on hydrogen. Only t he
equilibrium dat a produced by t hese correlat ions is used by UniSim
Design. The Lee- Kesler met hod is used for liquid and vapour ent halpies
and ent ropies.
Gener al NRTL This variat ion of t he NRTL model allows you t o select t he
equat ion format for equat ion paramet ers: t and o. Apply
t his model t o syst ems:
component s.
where you require simult aneous solut ion of VLE and
LLE, and t here exist s a wide boiling point or
Mar gul es This was t he first Gibbs excess energy represent at ion
developed. The equat ion does not have any t heoret ical
basis, but is useful for quick est imat es and dat a
int erpolat ion.
NRTL This is an ext ension of t he Wilson equat ion. I t uses
st at ist ical mechanics and t he liquid cell t heory t o
represent t he liquid st ruct ure. I t is capable of
represent ing VLE, LLE, and VLLE phase behaviour.
UNI QUAC Uses st at ist ical mechanics and t he quasi- chemical t heory
of Guggenheim t o represent t he liquid st ruct ure. The
equat ion is capable of represent ing LLE, VLE, and VLLE
wit h accuracy comparable t o t he NRTL equat ion, but
wit hout t he need for a non- randomness fact or.
v an Laar This equat ion fit s many syst ems quit e well, part icularly
for LLE component dist ribut ions. I t can be used for
syst ems t hat exhibit posit ive or negat ive deviat ions from
Raoult ' s Law, however, it cannot predict maxima or
minima in t he act ivit y coefficient . Therefore it generally
performs poorly for syst ems wit h halogenat ed
hydrocarbons and alcohols.
Wi l son First act ivit y coefficient equat ion t o use t he local
composit ion model t o derive t he Gibbs Excess energy
expression. I t offers a t hermodynamically consist ent
approach t o predict ing mult i- component behaviour from
regressed binary equilibrium dat a. However t he Wilson
model cannot be used for syst ems wit h t wo liquid
phases.
Model Descr i pt i on
Chao Seader Use t his met hod for heavy hydrocarbons, where t he
pressure is less t han 10342 kPa ( 1500 psia) , and
t emperat ures range bet ween - 17. 78 and 260C ( 0- 500F) .
Gr ay son
St r eed
Recommended for simulat ing heavy hydrocarbon syst ems
wit h a high hydrogen cont ent .
Act i v i t y Model Descr i pt i on
2- 11
Vapour Pressure Models
Vapour Pressure K- value models may be used for ideal mixt ures at low
pressures. I deal mixt ures include hydr ocarbon syst ems and mixt ures
such as ket ones and alcohols, where t he liquid phase behaviour is
approximat ely ideal. The models may also be used as first
approximat ions for non- ideal syst ems. The following vapour pressure
models are available:
Elect rolyt e Models
Miscellaneous Types
The Miscellaneous group cont ains Propert y Packages t hat are unique
Model s Descr i pt i on
Ant oi ne This model is applicable for low pressure syst ems t hat
behave ideally.
Br aun K10 This model is st rict ly applicable t o heavy hydrocarbon
syst ems at low pressures. The model employs t he Braun
convergence pressure met hod, where, given t he normal
boiling point of a component , t he K-value is calculat ed at
syst em t emperat ure and 10 psia ( 68. 95 kPa) .
Esso Tabul ar This model is st rict ly applicable t o hydrocarbon syst ems at
low pressures. The model employs a modificat ion of t he
Maxwell- Bonnel vapour pressure model.
Pr oper t y Pack age Descr i pt i on
I deal El ect r ol y t e This package was developed specifically for t he
alumina syst em. I n t his model, gas phase is
considered as ideal mixt ure and liquid phase as
ideal solut ion. The support ed component s by t his
model are only limit ed t o elect rolyt e- wat er
syst em.
NOTE: I f you at t ach component s ot her t han
elect rolyt e and wat er t o t his package or use t his
model for anot her purpose it may result in some
unexpect ed behaviour and result s.
Ur ea El ect r ol y t e
Pack age
Urea Elect rolyt e is an opt ional Propert y Package.
Cont act Honeywell for furt her informat ion.
2- 12
and do not fit int o t he groups previously ment ioned.
Component List Select ion
You must also select a Component List t o associat e wit h t he current
Fluid Package from t he Component List Select ion drop- down list .
Component List s ar e st ored out side of t he Fluid Package Manager in t he
Component s Manager and may cont ain t radit ional, hypot het ical, and
elect rolyt e component s.
Pr oper t y Pack age Descr i pt i on
Ami ne Pk g Cont ains t hermodynamic models developed by
D. B. Robinson & Associat es for t heir propriet ary
amine plant simulat or, AMSI M. You can use t his
propert y package for amine plant simulat ions wit h
UniSim Design.
Amines is an opt ional Propert y Package. Cont act
Honeywell for furt her informat ion.
ASME St eam Rest rict ed t o a single component , namely H2O.
Uses t he ASME 1967 St eam Tables.
Cl ean Fuel s Pk g
Uni Si m Desi gn
The Clean Fuels package is a unique propert y
package t o model clean fuel t echnology.
DBR Ami ne Pack age DBR Amine package is a version of Amine package
developed based on t he newer version of AMSI M
from D. B. Robinson & Associat e. This package is
developed based on UniSim Thermo I Ext ended
int erfaces.
I nf ochem Mul t i f l ash I nfochem Mult iflash is a UniSim Thermo ext ension
developed t o link t o Mult iflash t hermodynamic
engine from I nfochem I nc. Through t his ext ension,
UniSim can apply bot h propert y calculat ions and
flash calculat ions from Mult iflash t o UniSim whole
flowsheet .
NBS St eam Rest rict ed t o a single component , namely H2O.
Ut ilizes t he NBS 1984 St eam Tables.
Neot ec Bl ack Oi l I n UniSim Design, Black Oil describes a class of
phase behavior and t ransport propert y models.
Black oil correlat ions are t ypically used when a
limit ed amount of oil and gas informat ion is
available in t he syst em. Oil and gas fluid
propert ies are calculat ed from correlat ions wit h
t heir respect ive specific gravit y ( as well as a few
ot her easily measured paramet ers) .
OLI _El ect r ol y t e Developed by OLI Syst ems I nc. and used for
predict ing t he equilibrium propert ies of a chemical
syst em including phase and react ions in a wat er
solut ion.
I t i s not r ecommended f or user s t o at t ach t he Mast er
Component Li st t o any Fl ui d Pack age. I f onl y t he mast er l i st
ex i st s, by def aul t a cl oned v er si on of t he Mast er Component
Li st i s cr eat ed ( cal l ed Component Li st - 1) . Thi s l i st i s
sel ect ed i ni t i al l y w hen a new Fl ui d Pack age i s cr eat ed.
t he package see
Appendi x C - Ami nes
Pr oper t y Pack age.
t he OLI _Elect rolyt e
propert y package, refer
t o Sect i on 1. 6 -
Uni Si m Desi gn
OLI _El ect r ol y t e
Pr oper t y Pack age in
t he Uni Si m Desi gn OLI
I nt er f ace Ref er ence
Gui de.
2- 13
UniSim Design provides a warning message when you at t empt t o
associat e a Component List cont aining incompat ible and/ or not
recommended component s, wit h your proper t y package.
Also, if you swit ch bet ween propert y packages, and any component s
are incompat ible or not recommended for use wit h t he current proper t y
package, a view appears providing furt her opt ions ( see t he following
Warning Messages sect ion) .
Warning Messages
There ar e t wo different warning views t hat you may encount er while
modifying a Fluid Package. These sit uat ions arise when a Component
List is inst alled int o t he Fluid Package and you want t o select a new
propert y package. Some component s from t he select ed Component List
may eit her not be recommended or are incompat ible wit h t he new
propert y package select ion.
The first view involves t he use of Non- Recommended component s. I n
UniSim Design, you can select component s t hat are not recommended
for use wit h t he current pr opert y package. I f you t ry t o swit ch t o
anot her pr opert y package for which t he component s are not
recommended, t he following view appears:
The obj ect s from t he Component s Not Recommended for Propert y
Package view are described below:
Fi gur e 2. 6
Not
Recommended
The non- recommended component s are list ed in t his
group.
Desi r ed Pr op Pk g This field init ially displays t he Propert y Package for
which t he list ed component s are Not Recommended.
This field is also a drop- down list of all available
Propert y Packages so you may make an alt ernat e
select ion wit hout ret urning t o t he Fluid Package
propert y view.
2- 14
The second dialog involves t he use of I ncompat ible component s. I f you
t ry t o swit ch t o a pr opert y package for which t he component s are
incompat ible, t he following view appears:
The Obj ect s from t he Component s I ncompat ible wit h Propert y Package
view are described below:
Addit ional Propert y Package Opt ions
When you have select ed a Proper t y Package, addit ional informat ion and
opt ions may be displayed on t he right side of t he Set Up t ab. This
informat ion is direct ly relat ed t o t he Propert y Package t ype select ed.
I n t his sect ion, t he addit ional informat ion displayed wit h t he propert y
met hod select ion is discussed. The groups t hat are encount ered are
shown below. I t should be not ed t hat not all EOSs or Act ivit y models
Act i on This group box cont ains t wo radio but t ons:
Del et e Component s. This removes incompat ible
component s from t he Fluid Package.
Keep Component s. This keeps t he component s
in t he Fluid Package.
OK Accept s t he Desired Prop Pkg wit h t he appropriat e
Act ion.
Cancel Ret urn t o t he Prop Pkg t ab wit hout making changes.
Fi gur e 2. 7
I ncompat i bl e
Component s
The incompat ible component s are list ed in t his group.
Desi r ed Pr op Pk g This field init ially displays t he Propert y Package for
which t he list ed component s are I ncompat ible.
This field is also a drop- down list of all available
Propert y Packages so you may make an alt ernat e
select ion wit hout ret urning t o t he Fluid Package
propert y view.
OK This but t on accept s t he Desired Prop Pkg wit h t he
appropriat e Act ion ( i. e., delet e t he incompat ible
component s) .
Cancel Press t his but t on t o keep t he current Propert y Package
2- 15
include t he specificat ions indicat ed.
EOS Ent halpy Met hod Specificat ion
The Lee- Kesler Plocker ( LKP) and Zudkevit ch Joffee ( ZJ) propert y
packages bot h use t he Lee- Kesler ent halpy met hod. You cannot change
t he ent halpy met hod for eit her of t hese Equat ions of St at e ( in ot her
words, t he figure below does not appear) .
Wit h any ot her Equat ion of St at e, you have a choice for t he ent halpy
met hod as described below:
Peng Robinson Opt ions
The Peng Robinson opt ions ar e only available when t he Peng Robinson
Pr oper t y Pack ages Speci f i cat i ons and Opt i ons
Equat i on of St at es EOS Ent hal py Met hod Speci f i cat i on , Peng
Robi nson Opt i ons, EOS Densi t y and Smoot h
Li qui d Densi t y Speci f i cat i ons
Act i v i t y Model s Act i v i t y Model Speci f i cat i ons
Ami ne Pk g Ami ne Opt i ons:
Thermodynamic Models for Aqueous Amine
Solut ions
Vapour Phase Model
OLI _El ect r ol y t e OLI _El ect r ol y t e Opt i ons:
I nit ialize and View Elect rolyt es
Phase and Solid opt ions
Mul t i pl e Pack ages Cheuh & Prausnit z liquid compressibilit y
correlat ion specificat ions for all UniSim Design
nat ive packages except MBWR, ASME St eam, NBS
St eam and OLI _Elect rolyt e.
Fi gur e 2. 8
Ent hal py Met hod Descr i pt i on
Equat i on of St at e Wit h t his radio but t on select ion, t he ent halpy met hod
cont ained wit hin t he Equat ion of St at e is used.
Lee- Kesl er The Lee- Kesler met hod is used for t he calculat ion of
ent halpies. This opt ion result s in a combined Propert y
Package, employing t he appropriat e equat ion of st at e
for vapour- liquid equilibrium calculat ions and t he Lee-
Kesler equat ion for t he calculat ion of ent halpies and
ent ropies. This met hod yields comparable result s t o
UniSim Design' st andard equat ions of st at e and has
ident ical ranges of applicabilit y.
Lee- Kesler ent halpies
may be slight ly more
accurat e for heavy
hydrocarbon syst ems,
but require more
comput er resources
because a separat e
model must be solved.
2- 16
propert y package is select ed.
The opt ions are explained in t he t able below:
EOS Densit y and Smoot h Liquid Densit y
Specificat ions
The Use EOS Densit y and Smoot h Liquid Densit y checkboxes affect t he
PR, PRSOUR, SRK, and SRKSOUR propert y packages. I n pr evious
versions t o UniSim Design, t hese propert y packages used t he Cost ald
liquid densit y model. This met hod was only applied when t he reduced
t emperat ure ( Tr) was less t han unit y. When t he reduced t emperat ure
exceeded unit y, it swit ched t o t he EOS liquid densit y. Hence, at Tr= 1
t here is a shar p change ( discont inuit y) in t he liquid densit y causing
problems especially in dynamics mode.
For older cases including Legacy HYSI M cases, t he densit y smoot hing
opt ion is not select ed. This means t hat liquid densit ies in cases using
t he smoot hing opt ion may differ fr om t hose cases in t he past .
By default , new cases have t he densit y smoot hing opt ion select ed and
EOS densit y not select ed, which is t he recommended opt ion. By default ,
or if t he smoot hing opt ion is select ed, UniSim Design int erpolat es t he
liquid densit ies from Tr= 0. 95 t o Tr = 1. 0, giving a smoot h t ransit ion. I t
should be not ed t hat t he densit ies differ if t he opt ion is not select ed.
I f bot h t he Use EOS Densit y and Smoot h Liquid Densit y boxes are not
select ed, t he behaviour and result s are t he same as befor e ( previous t o
UniSim Design) and can cause problems as discussed earlier.
Fi gur e 2. 9
Opt i on Descr i pt i on
Uni Si m
Desi gn
The UniSim Design PR EOS is similar t o t he PR EOS wit h several
enhancement s t o t he original PR equat ion. I t ext ends it s range
of applicabilit y and bet t er represent s t he VLE of complex
syst ems.
St andar d This is t he st andard Peng Robinson ( 1976) equat ion of st at e, a
modificat ion of t he RK equat ion t o bet t er represent t he VLE of
nat ural gas syst ems accurat ely.
propert y packages, refer
t o Appendi x A.3.1 -
Equat i ons of St at e.
Cost ald t ypically gives
bet t er liquid densit ies
and smoot hing near
Tr= 1 is common.
2- 17
Glycol and Twu Packages Specificat ion
There is a special opt ion for TST, PRTwu, SRKTwu and GLYCOL
packages, shown as checkbox Use Fi x ed TcPc f or TEG. This checkbox
will come up only aft er choose Glycol and Twu packages. By default ,
t his checkbox is unselect ed.
This checkbox is used t o let user opt ionally specify crit ical propert ies for
TEG. I f t he box is checked, t hose reliable crit ical t emperat ure and
pressure of TEG in pure component dat abase will be used. Ot herwise,
t he special Twu crit ical propert ies of TEG will be used as before.
Act ivit y Model Specificat ions
The Act ivit y Model Specificat ion group appears for each act ivit y model.
There ar e t hree specificat ion it ems wit hin t his group as shown in t he
following figure.
Act ivit y Models only perform calculat ions for t he liquid phase, t hus, you
are required t o specify t he met hod t o be used for solving t he vapour
phase. The first field in t he Act ivit y Model Specificat ions group allows
you t o select an appropriat e Vapour Model for your fluid package.
The list of vapour phase models are accessed t hrough t he drop- down
Fi gur e 2. 10
Fi gur e 2. 11
2- 18
list and are described below.
The second field in t he Act ivit y Model Specificat ions group is t he
UNI FAC Est imat ion Temp. This t emperat ure is used t o est imat e
int eract ion paramet ers using t he UNI FAC met hod. By default , t he
t emperat ure is 25C, alt hough bet t er result s are achieved if you select
a t emperat ure t hat is closer t o your ant icipat ed operat ing condit ions.
The t hird field in t his gr oup is a checkbox for t he Poynt ing Correct ion.
This checkbox t oggles t he Poynt ing correct ion fact or, which by default ,
is act ivat ed. The cor rect ion fact or is only available for vapour phase
models. The correct ion fact or uses each component ' s molar volume
( liquid phase) in t he calculat ion of t he overall compressibilit y fact or.
Anot her special opt ion Mak e H2S as Condensabl e Component will
appear only aft er choosing t he NRTL package. By default , t his checkbox
is unselect ed.
I deal The UniSim Design default . I t is applied for cases in which
you are operat ing at low or moderat e pressures.
RK The generalized Redlich Kwong cubic equat ion of st at e is
based on reduced t emperat ure and reduced pressure, and is
generally applicable t o all gases.
Vi r i al Enables you t o bet t er model t he vapour phase fugacit ies of
syst ems t hat display st rong vapour phase int eract ions.
Typically t his occurs in syst ems cont aining carboxylic acids,
or ot her compounds t hat have t he t endency t o form st able
hydrogen bonds in t he vapour phase.
PR Uses t he Peng Robinson EOS t o model t he vapour phase.
Use t his opt ion for all sit uat ions t o which PR is applicable.
SRK Uses t he Soave Redlich Kwong EOS t o model t he vapour
phase. Use t his opt ion for all sit uat ions t o which SRK is
applicable.
HF- PR Uses t he Peng Robinson EOS t o model t he vapor phase wit h
special t reat ment for Hydrogen Fluoride - HF.
Fi gur e 2. 12
2- 19
This checkbox is used t o allow t he user t he opt ion of specifying H2S as
a Condensable or Non- Condensable component . I f select ed, t he H2S
will be t aken as a Condensable component in calculat ion. Ot herwise,
H2S will be t aken as Non- Condensable.
Amine Opt ions
The following Amine opt ions are available when t he Amine pkg is
select ed.
The Thermodynamic Models for Aqueous Amine Solut ions allows you t o
select bet ween t he Kent - Eisenber g and Li- Mat her models. The Vapour
Phase Model group allows you t o select bet ween I deal and Non- I deal
models.
OLI _Elect rolyt e Opt ions
I f t he OLI _Elect rolyt e propert y package is select ed for t he fluid
package, t he following elect rolyt e opt ions appear on t he right side of
t he view.
Aft er select ing elect rolyt e component s for a component list fr om t he
dat abase, a elect rolyt e syst em is est ablished. The init ialize Elect rolyt es
Environment but t on is used for t he following:
Generat ing a group of addit ional component s based on t he
select ed component s and t he set t ing in Phase Opt ion and Solid
Opt ion below.
Fi gur e 2. 13
Fi gur e 2. 14
Refer t o t he Appendi x
C. 4 - Equi l i br i um
Sol ubi l i t y for det ailed
informat ion on each
t hermodynamic model.
Refer t o t he Uni Si m
elect rolyt es.
2- 20
Generat ing a corresponding Chemist ry model for
t hermodynamic calculat ion.
The phase opt ion includes t he vapour, organic, solid, and aqueous
phases. The checkboxes allow you t o select t he mat erial phases t hat
are considered during t he flash calculat ion. The vapour, organic and
solid phases, may be included or excluded from calculat ions. The
aqueous phase must be included in all elect rolyt e simulat ions and is not
accessible. By default , t he vapour and solid phases are select ed wit h
t he organic phase unchecked.
The flexibilit y of select ing different phase combinat ions and t he
procedure for phase mixing used by t he flash calculat ion is described in
t he following t able:
The Solid Opt ion group includes t wo checkboxes and t he Select ed Solid
but t on. UniSim Design allows you t o exclude all solids in your case by
select ing t he Exclude All Solids checkbox. I t also allows you t o exclude
solid component s individually when t he solid phase is included by
disabling solid component s t hat are not of int erest in t he simulat ion. To
do t his, you must invoke I nit ialize Elect rolyt es Environment first , and
t hen click t he Select ed Solid but t on. When you click t he but t on, you can
select any component t hat you want t o be included or excluded in all of
t he Elect r olyt e st reams from t he case. When t he solid component s are
excluded, you have t o re- init ialize t he Elect rolyt es Environment .
I f you select t he All Scaling Tendency checkbox, all solids are excluded
from t he case, but t he Scaling Tendency I ndex is st ill calculat ed in t he
flash calculat ion.
The View Elect rolyt e React ion in Trace Window but t on is act ivat ed when
Phases I ncl uded Descr i pt i on of t he Fl ash Act i on
Vapour and Sol i d Generat es vapour and solid phases when t hey exist . I f
an organic phase appears, it is included in t he vapour
phase.
Or gani c and
Sol i d
Generat es t he organic and solid phase when t hey exist .
I f a vapour phase appears, it is included in t he organic
phase.
Vapour and
Or gani c
Generat es t he vapour and organic phase when t hey
exist . I f a solid phase appears, it is included in t he
aqueous phase.
Vapour onl y Generat es t he vapour phase when it exist s. I f an
organic phase appears, it will be included in t he vapour
phase and if a solid phase appears, it is included in t he
aqueous phase.
Or gani c Onl y Generat es t he organic phase when it exist s. I f a vapour
phase appears, it will be included in t he organic phase
and if a solid phase appears, it is included in t he
aqueous phase.
Sol i d Onl y An elect rolyt e case wit h no organic or vapour phase is
impossible and is not be accept ed.
Refer t o Sect i on 1. 6. 6 -
Di sabl i ng Sol i d
Component s in t he
Uni Si m Desi gn OLI
Gui de for more
informat ion on including
and excluding solids.
Scal i ng Tendenci es of
t he Uni Si m Desi gn OLI
Gui de for more
informat ion on scaling
t endencies.
2- 21
t he Elect r olyt es Environment is init ialized. I t allows you t o view what
react ion( s) are involved in t he Thermo flash calculat ion in t he t race
window.
Cheuh & Prausnit z Correlat ion Specificat ions
The checkbox Cor r ect ed Cheuh and Pr ausni t z cor r el at i on is applied
t o correct UniSim Design Cheuh & Prausnit z liquid compressibilit y
correlat ion met hod. I t will affect t he liquid densit y calculat ion result s
for all UniSim Design nat ive pr opert y packages except MBWR, ASME
St eam, NBS St eam and OLI _Elect rolyt e.
The check box shows in t he pr opert y package views as below when
UniSim Design nat ive propert y packages ar e select ed ( except MBWR,
ASME St eam, NBS St eam and OLI _Elect rolyt e) .
The basis of t he Cheuh & Prausnit z correlat ion for t he densit y of
compress liquid is
where
The previous version of UniSim Design applied t he it em ( 1- 0. 90w) in
t he above equat ion, which act ually should be . So, if
Fi gur e 2. 15
( 2. 1)
9 / 1
0
0
) (
9
1
(
+ = P P
P
N z
C
C
N 1 0.9 w ( ) 6.9547 76.2853T

R
191.306T
R
2
82.7631T
3
R 82.7631T
R
4
+ + + ( ) exp =
1 0.89 W ( )
2- 22
Cor r ect ed Cheuh and Pr ausni t z cor r el at i on is checked, t he
correlat ion is correct ed by changing t he it em t o .
When creat ing new cases, t his checkbox will be checked by default t o
correct t he Cheuh & Prausnit z correlat ion. But for t he old cases built in
t he previous version of UniSim Design, t he check box will be set t o
unchecked by default , in order t o not affect t he old cases.
Special Treat ment for Wat er
The Speci al Tr eat ment f or w at er checkbox affect s Peng Robi nson
and Sour PR propert y packages. When t his checkbox is checked it
applies values for cert ain paramet ers used in t he calculat ion of t he
alpha funct ion for wat er depending on if t he square root of t he reduced
t emperat ure value is less t han 0. 922 or great er. I f t he checkbox
remains unchecked, t he amix paramet er used in t he calculat ion of alpha
funct ion is calculat ed as a funct ion of t he component accent ricit y ( using
a polynomial) as is done for ot her library component s.
I n t he previous version of UniSim Design by default t he special
t reat ment for wat er was not t he default opt ion for new caes. This
applicat ion caused discont inuit ies in t he predict ion of t he VLE for cert ain
cases when wat er dominat ed t he fluid syst em being simulat ed. For
older cases t han R390 t he special t reat ment for wat er is always applied.
This means t hat t he VLE for wat er may differ from t hose cases in t he
past .
By default t he special t reat ment for wat er checkbox is checked which is
t he recommended opt ion. I f t his check box is select ed, t he behavior
and result s are t he same as before ( previous t o UniSim Design) and can
cause problems as discussed earlier.
2. 4. 2 Paramet ers Tab
The informat ion and opt ions displayed on t he Paramet ers t ab is
dependent on t he Propert y Package select ion. Some Pr opert y Packages
have not hing on t he Paramet ers t ab, while ot hers display addit ional
informat ion required. Those Propert y Packages which have informat ion
on t he Paramet ers t ab are ment ioned in t his sect ion.
I f a value is est imat ed by UniSim Design, it is indicat ed in red and can
be modified.
1 0.89 W ( )
2- 23
GCEOS ( Generalized Cubic EOS)
The Generalized Cubic Equat ion of St at e ( GCEOS) is an alt er nat ive t o
t he st andard equat ion of st at e propert y packages. I t allows you t o
define and cust omize t he cubic equat ion t o your own specificat ions.
Generalized Cubic Equat ion of St at e
To gain an underst anding of how t o specify t he GCEOS propert y
package Paramet ers t ab, you must first consider t he general cubic
equat ion of st at e form:
OR
Fi gur e 2. 16
( 2. 2)
( 2. 3)
P
RT
v b
--------
a T ( )
v
2
ubv wb
2
+ +
--------------------------- =
Z
3
C
1
Z
2
C
2
Z C
3
+ + + 0 =
2- 24
where:
MR
ij
= t he mixing rule
To calculat e t he values of b
i
and a
c
, t he cubic equat ion, Equat i on
( 2.13) , is solved t o find a value for .
The value of a
i
in Equat i on ( 2.10) requires you t o use t he o t erm.
o in t urn is made up of t he k t erm. The paramet er k is a polynomial
equat ion cont aining five paramet er s: k
0
, k
1
, k
2
,

k
3
,

k
4
and

k
5
. The
paramet er k
0
is also represent ed by a polynomial equat ion consist ing of
( 2. 4)
( 2. 5)
( 2. 6)
( 2. 7)
( 2. 8)
( 2. 9)
(2.10)
(2.11)
(2.12)
(2.13)
(2.14)
C
1
Bu B 1 =
C
2
B
2
w B
2
u Bu A + =
C
3
B
3
w B
2
w AB + + ( ) =
Z
Pv
RT
----- =
A
a
mix
P
R
2
T
2
---------- =
B
b
mix
P
RT
---------- =
a
mix
x
i
x
j
a
i
T ( )a
j
T ( ) MR
ij

=
b
mix
x
i
b
i
=
a
i
T ( ) a
c
o =
a
c
3 u w ( )
2
+
3 u 1 ( ) +
------------------------ u +
\ .
| |
RT
c
V
c
=
b
i
V
c
=
u w u + ( ) w | |
3
3 w u + ( )
2
3 1 + + 0 =
o T ( ) 1 k 1 T
R
0.5
( ) + | |
2
=
2- 25
4 paramet ers ( A, B, C and D) .
The Paramet ers t ab for t he GCEOS consist s of t hree group boxes:
GCEOS Pure Component Paramet ers
GCEOS Paramet ers
I nit ialize EOS
GCEOS Pure Component Paramet ers Group
This group allows you t o define o by specifying t he values of k
0
- k
5
.
To specify t he value of k
0
, select t he kappa0 radio but t on and a view
similar t o t he one shown in Fi gur e 2. 17 should appear. The group
consist s of a mat rix cont aining 4 paramet ers of Equat i on ( 2.16) : A, B,
C, and D for each component select ed in t he Fluid Package.
To specify t he remaining kappa paramet ers ( i. e., k
1
- k
5
) , select t he
kappa1- 5 radio but t on. A new mat rix appears in t he GCEOS Pure
(2.15)
(2.16)
Fi gur e 2. 17
k k
0
k
1
k
2
k
3
T
R
( ) 1 T
R
k
4
( ) + | | 1 T
R
0.5
+ ( ) 0.7 T
R
( ) T
k
5
+ =
k
0
A Be Ce
2
De
3
+ + + =
2- 26
Component Paramet ers group.
This mat rix allows you t o specify t he k values for each component in t he
Fluid Package.
Volume Translat ion
The GCEOS allows for volume t ranslat ion correct ion t o provide a bet t er
calculat ion of liquid volume by t he cubic equat ions of st at e. The
correct ion is simply a t ranslat ion along t he volume axis, which result s
in a bet t er calculat ion of liquid volume wit hout affect ing t he VLE
calculat ions. Mat hemat ically t his volume shift is represent ed as:
where:
= t ranslat ed volume
= is t he t ranslat ed cubic equat ion of st at e paramet er
c
i
= t he pure component t ranslat ed volume
x
i
= t he mole fract ion of component i in t he liquid phase.
The result ing equat ion of st at e appears as shown in Equat i ons ( 2. 5) ,
( 2.6) and ( 2. 7) wit h b and v replaced wit h t he t ranslat ed values (
and ) .
Fi gur e 2. 18
(2.17)
(2.18)
v v x
i
c
i
i 1 =
n
+ =
b
b x
i
c
i
i 1 =
n
+ =
v
b
v
b
2- 27
To specify t he value of t he pure component correct ion volume, c
i
, select
t he Vol. Translat ion radio but t on. A view similar t o t he one shown in
Fi gur e 2. 19 will appear.
The GCEOS Pure Component s Paramet ers group now cont ains a mat rix
cont aining t he volume correct ion const ant s for each component
current ly select ed. The mat rix should init ially be empt y. You may ent er
your own values int o t his mat r ix or you may click t he Est imat e but t on
and have UniSim Design est imat e values for you. c
i
is est imat ed by
mat ching liquid volume at normal boiling point t emperat ure wit h t hat of
t he liquid volume obt ained from an independent met hod ( COSTALD) . I f
normal boiling point t emperat ure is missing, 0. 7Tc ( crit ical
t emperat ure) will be used t o est imat e c
i
.
UniSim Design only est imat es t he correct ion volume const ant for t hose
component s whose cells have no value ( i. e., t hey cont ain 0. 000) . I f you
specify one value in t he mat rix and click t he Est imat e but t on, you are
only est imat ing t hose empt y cells.
GCEOS Paramet ers Group
The GCEOS Paramet ers group allows you t o specify t he u and w
paramet ers found in Equat i ons ( 2. 4) t o ( 2. 16) .
The following t able list s t he u and w values for some common equat ions
of st at e:
Fi gur e 2. 19
EOS u w
van der Waal s 0 0
Redl i ch- Kw ong 1 0
Peng- Robi nson 2 - 1
To est imat e a cell
cont aining a previously
ent ered value, select t he
cell, delet e t he current
value and click t he
Est i mat e but t on.
2- 28
Equat ion St at us Bar
The GCEOS Paramet er group also cont ains t he Equat ion St at us Bar. I t
t ells you t he st at us of t he equat ion definit ion. There are t wo possible
messages and are described as follows:
I nit ialize EOS
The I nit ialize EOS drop- down list allows you t o init ialize GCEOS
Paramet ers t ab wit h t he default values associat ed wit h t he select ed
Equat ion of St at e.
The four opt ions available are as follows:
van der Waals Equat ion
SRK Equat ion
PR Equat ion
PRSV Equat ion
Glycol Propert y Package
The following opt ions appear on t he Paramet ers t ab when t he
Glycol propert y package is select ed:
Ent halpy
Densit y
Use Wat er Gas kij
Glycol EOS Mixing Rule
Message Descr i pt i on
This message appears if poor values are chosen for u
and w.
I f t he values select ed for u and w are suit able t his
message appears.
2- 29
Ent halpy
The Glycol package offers t wo opt ions for Ent halpy.
Densit y
The four opt ions for Densit y are Use EOS Densi t y, COSTALD
( default ) , Use UOP Densi t y, and Modi f i ed COSTALD.
COSTALD
When COSTALD or Modi f i ed COSTALD is select ed, t he Smoot h
Li qui d Densi t y checkbox will appear in t he Paramet ers area. This
checkbox is select ed as t he default .
Fi gur e 2. 20
Ent hal py Met hod Descr i pt i on
Equat i on of St at e The ent halpy met hod cont ained wit hin t he Equat ion
of St at e is used.
Lee- Kesl er Lee- Kesler met hod is used for calculat ing ent halpy,
result ing in a combined Propert y Package,
employing t he appropriat e equat ion of st at e for
vapour- liquid equilibrium calculat ions and t he Lee-
Kesler equat ion for t he calculat ion of ent halpies and
ent ropies.
Lee- Kesler ent halpies may be slight ly more accurat e
for heavy hydrocarbon syst ems, but require more
comput er resources because a separat e model must
be solved.
2- 30
Glycol EOS Mixing Rule
The t hree opt ions for Glycol EOS Mixing Rule ar e Use I nf i ni t e
Pr essur e ( default ) and Use Zer o Pr essur e.
Kabadi Danner
The Kabadi Danner Pr opert y Package uses Group Paramet ers t hat are
aut omat ically calculat ed by UniSim Design. The values are generat ed
from Twu' s met hod.
Peng- Robinson EOS
Peng- Robinson is an ext ensively used propert y package. This page
provides volume t ranslat ion calculat ions and BI P ( Binary I nt eract ion
paramet ers) paramet eres for Peng- Robinson pr opert y package.
Volume t ranslat ion correct ion result s in bet t er calculat ion of liquid
volume by cubic equat ion of st at e. The correct ion is simply a t ranslat ion
along t he volume axis, which result s in a bet t er calculat ion of liquid
volume wit hout affect ing t he VLE calculat ions. Mat hemat ically, t his
volume shift is expressed as:
where: = t ranslat ed volume
= t he pure component t ranslat ed volume
= t he mole fract ion of component i in t he liquid phase.
To specify t he pure component correct ion volume, c
i
, select Use EOS
Densi t y from t he Densit y dr opdown as shown in t he following figure. A
Fi gur e 2. 21
(2.19)
=
+ =
n
i
i i
c x v v
1
~
v
~
i
c
i
x
2- 31
view having volume t ranslat ion paramet er t able will appear in t he
Paramet ers group.
The PREOS Pure Component s Paramet er s group now cont ains a mat rix
cont aining t he volume correct ion const ant s for each component
current ly select ed. The mat rix should init ially be empt y. You may ent er
your own values int o t his mat r ix or you may click t he Est imat e but t on
and have UniSim Design est imat e values for you. c
i
is est imat ed by
mat ching liquid volume at normal boiling point t emperat ure wit h t hat of
t he liquid volume obt ained from an independent met hod ( COSTALD) .
Use UOP Densit y Opt ion
As shown in Fi gur e 2.23 t here is anot her densit y calculat ion opt ion
Use UOP Densi t y in t he Densit y row of opt ions group.
Fi gur e 2. 22
Fi gur e 2. 23
2- 32
This opt ion is using t he special met hod t hat is supplied by UOP t o
calculat ion liquid densit y. This opt ion does not handle smoot h liquid
densit y calculat ion. Aft er select ing t his opt ion, t he smoot h liquid densit y
checkbox will be disabled on Set Up page. The UOP densit y opt ion will
be available for following PR t ype packages:
Peng- Robinson
SoaveRK
Sour PR
Sour SRK
PRTwu
SRKTwu
TSTPR
Glycol
Modified COSTALD Opt ion
I n UniSim Design, COSTALD is a widely used met hod t o calculat e liquid
densit y of compressed liquids. I t can be split int o t wo part s. One is t he
calculat ion of t he sat urat ed liquid densit y and t he ot her one is t he
compressibilit y correct ion. The sat urat ed liquid densit y is t hen correct ed
wit h a pressur e dependence equat ion t o predict t he change of densit y
when t he pressure is increased from t he sat urat ed pressure t o t he
act ual pressur e.
Hence t he sat urat ed pressure calculat ion is crit ical t o t he accuracy of
t he liquid densit y calculat ion. I n Modified COSTALD, compared wit h
legacy COSTALD met hod, a different correlat ion fr omt ext by Poling,
Prausnit z and O' Connell ( 2001)
2
is implement ed t o calculat e t he
sat urat ed pressure. At first t he crit ical pressure is est imat ed by:
Then t he reduced pressure is obt ained from a generalized Riedel vapor
pressure equat ion which wit h some algebraic manipulat ion, can be put
(2.20)
( )
cm
cm SRKm
cm
V
RT
P
e 080 . 0 291 . 0
=
2- 33
in t he form:
Wit h t he compressibilit y correct ion, a modified correlat ion is also
implement ed in Modified COSTALD in order t o ext end t he range for
non- polar liquids. The basis of t he correlat ion for t he densit y of
compressed liquid is
where:
The UOP densit y opt ion and Modified COSTALD opt ion will be available
for following PR t ype packages:
Peng- Robinson
SoaveRK
Sour PR
Sour SRK
PRTwu
SRKTwu
TSTPR
Glycol
(2.21)
(2.22)
1 0
ln
vpr vpr vpr
P P P e + =
6 0
17518 . 0 ln 55663 . 1
30662 . 6
13144 . 6
rm rm
rm
vpr
T T
T
P + =
6 1
08560 . 0 ln 26573 . 1
08508 . 3
99938 . 2
rm rm
rm
vpr
T T
T
P + + =
vpr cm vp
P P P =
( )
9 / 1
0
0
9
1
(
+ = P P
P
N Z
c
c
( ) ( ) ( ) ( ) ( ) ( )
4143 . 1 2 2
1 / 0017 . 0 0111 . 0 0038 . 0 exp 1 0617 . 4 2010 . 0 3066 . 1 exp
r r r
T T T N + + = e e e
2- 34
Est imat e Vol. Trans.
UniSim Design only est imat es t he correct ion volume const ant for t hose
component s whose cells have no value ( i. e., t hey cont ain 0. 000) . I f you
specify one value in t he mat rix and click t he Est imat e but t on, you are
only est imat ing t hose empt y cells.
COSTALD - c
i
is est imat ed by mat ching EOS volume at normal boiling
point and normal pressure wit h t hat of t he liquid volume obt ained using
COSTALD correlat ion at t he same t emperat ure and pressure condit ion.
RACKETT - c
i
is est imat ed by mat ching EOS volume at normal boiling
point and normal pressure wit h t hat of t he liquid volume obt t ained
using RACKETT cor relat ion at t he same t emperat ure and pressure
condit ion.
Modify H2 Tc and Pc Opt ion
When Modi f y H2 Tc and Pc is select ed, t he crit ical t emperat ure and
pressure of hydrogen is modified as a funct ion of t emperat ure. This
feat ure produces bet t er result s for simulat ion syst ems cont aining
hydrogen.
I ndexed Viscosit y Opt ion
The I ndexed Viscosit y opt ion enables you t o t oggle bet ween t wo
Fi gur e 2. 24
To est imat e a cell
cont aining a previously
ent ered value, select t he
cell, delet e t he current
value and click t he
Est i mat e but t on.
2- 35
met hods/ rules used t o calculat e t he blended liquid viscosit y.
When you select I ndex ed Vi scosi t y, t he Viscosit y I ndex Paramet ers
propert y view t hat is associat ed t o t he act ive fluid package appears.
I n t he Viscosit y I ndex Paramet ers group, you specify t he value for each
of t he t hree paramet ers used in t he linearized viscosit y calculat ion. The
equat ion below t he t able displays how each paramet er is used in t he
Twu and Bulls ( 1981)
2
calculat ion.
Theory
Viscosit y cannot be blended linearly, so a met hodology is adopt ed t hat
UniSim Design Viscosit y Provides an est imat e of t he apparent liquid
viscosit y of an immiscible hydrocarbon liquid-
aqueous mixt ure using only t he viscosit y and t he
volume fract ion of t he hydrocarbon phase
I ndexed Viscosit y Uses a linearized viscosit y equat ion from Twu and
Bulls.
Fi gur e 2. 25
2- 36
subst it ut es a funct ion of t he measured viscosit y t hat is approximat ely
linear wit h t emperat ure. A linearized equat ion for viscosit y is given by
Twu and Bulls ( 1981)
2
:
where:
T = absolut e t emperat ure R
v = kinemat ic viscosit y in cSt
Viscosit y index of component i can be simplified according t o t he above
equat ion:
where:
A = const ant at a fixed t emperat ure
visc( i) = kinemat ic viscosit y of component i in cSt
C = adj ust able paramet er
B = const ant
Viscosit y I ndex of a st ream:
where:
x( i) = mass fract ion of component i in t he st ream
Calculat ed kinemat ic viscosit y ( cSt ) of t he st ream:
(2.23)
(2.24)
(2.25)
(2.26)
10 10 log ( ( ) v 0.7 + ( ) ) log m 10T b + log =
vi i ( ) A 10 10 visc i ( ) C + ( ) log ( ) log B + =
vi Sum x i ( ) vi i ( ) ( ) =
v = 10^ (10 ^ ((vi- B)/A)) C
2- 37
Pure Component
UniSim Design calculat es t he viscosit y of a pure compound based on
t he component class designat ion as well as t he phase in which t he
component is present as well as a t emperat ure range:
Each viscosit y model is based on t he corresponding st at es principle. A
complet e descript ion of t he corresponding st ages NBS model used for
viscosit y predict ion used by Ely and Hanely is given in t he NBS
publicat ion
3
. This model was modified t o eliminat e t he it erat ive
procedure for calculat ing t he syst em shape fact ors. The generalized
Leech- Leland shape fact or models have been replaced by component
specific models.
Alt hough t he modified NBS models handles most hydrocarbons well,
t he Twu met hod is known t o do a bet t er j ob of predict ing t he viscosit y
of heavy hydrocarbon liquids. The Twu model is also based on t he
corresponding st at es pr inciple and uses a viscosit y correlat ion for n-
alkanes as it s reference fluid inst ead of met hane.
Experiment al viscosit y curves can be supplied via hypot het ical
propert ies or user dat a in UniSim Design direct ly by mapping t he library
component as a hypot het ical.
Not es:
1. Choose const ant C such t hat v i sc( i ) + C i s > 1.
Log10( Log10( v i sc( i ) + C) ) becomes i ndet er mi nat e
ot her w i se.
2. Const ant A and B do not af f ect t he cal cul at ed
v i scosi t y . They af f ect t he v i scosi t y i ndex onl y . Thi s
i s t he nat ur e of t he equat i ons. Choose A and B
w i sel y t o mat ch v i scosi t y i ndex . Choose C w i sel y t o
mat ch k i nemat i c v i scosi t y .
Syst em Vapor Li qui d
Light HCs ( NBP< 155F) Modified Ely and Hanley Ely and Hanely
Heavy HCs Modified Ely and Hanley Twu
Modified Let sou- St iel Modified Ely and Hanely Modified Let sou- St iel
Est i mat i ons f or vi scosi t y can be f ur t her i mpr oved ov er
i nt er nal est i mat i on r out i nes by suppl y i ng t he ex per i ment al
vi scosi t y f or a hy pot het i cal component .
2- 38
BI P ( Binary I nt eract ion Paramet er) Paramet er
I n legacy BI P syst em, t her e ar e special t reat ment s for BI P est imat ion in
Peng- Robinson package. Only few component pairs are special t reat ed.
The following is t he det ail infor mat ion for t he BI P special t reat ment in
Peng- Robinson package.
Fi gur e 2. 26
Speci al Tr eat ment f or H2O i n Peng- Robi nson
( When Est i mat ed HC- HC/ Set Non HC- HC t o 0.0 r adi o but t on i s sel ect ed )
Component Pai r BI P For mul at i on
H2O - TEGlycol
H2O DEGlycol
H2O - N2
H2O - CO2
H2O - H2S
H2O ( C1 / C2) ( if kij = 0.0 or 0. 5)
H2O Hydrocarbon ( if kij = 0.0 or 0. 5)
T k
ij
00135 . 0 0447 . 1 + =
T e k
ij
4 90130 . 4 341311 . 0 + =
( )T T k
ij
5 - -0.4686e 2 - 0.6700e -2.2380 + + =
( ) T T k
ij
+ + = 05 - -0.1274e 02 - 0.1879e -0.5572
( ) T T k
ij
+ + = 05 - -0.1142e 02 - 0.1565e -0.3896
5 . 0 =
ij
k
48 . 0 =
ij
k
2- 39

Speci al Tr eat ment f or TEGl y col i n Peng- Robi nson
TEGlycol Toluene
TEGlycol- Benzene
TEGlycol- Et hylbenzene
TEGlycol ( o-Xylene / m-Xylene / p-
Xylene)
Speci al Tr eat ment f or DEGl y col i n Peng- Robi nson
DEGlycol- CO
2
DEGlycol- H
2
S
DEGlycol Hydrocarbons
DEGlycol Met hane
if
if
if
DEGlycol ( Benzene/ Toluene/ E-
Benzene, o-Xylene/ m-Xylene/ p-
Xylene)
( ) T k
ij
44 . 691 19285 . 0 exp =
( ) T k
ij
7 . 1012 46717 . 0 exp =
( ) T k
ij
91 . 739 10433 . 0 exp =
( ) T k
ij
23 . 706 08432 . 0 exp =
T k
ij
4 2
10 0 . 5 10 9075 . 5

+ =
035 . 0 =
ij
k
40 . 0 =
ij
k
21 . 0 =
ij
k
15 . 298 s T
25 . 0 =
ij
k
15 . 323 > T
T e k
ij
3 6 . 1 26704 . 0 + =
( ) 15 . 323 15 . 298 < < T
09 . 0 =
ij
k
2- 40
The Peng- Robinson BI P Special Treat ment group allows you have a
choice for t he special t r eat ment for BI P as described below:
Peng- Robinson St ryj ek Vera ( PRSV)
PRSV uses an empirical fact or, Kappa, for fit t ing pure component
vapour pressures.
Zudkevit ch Joffee
This Pr opert y Package uses a b zero Paramet er. UniSim Design set s t he
Fi gur e 2. 27
BI P Speci al Tr eat met Descr i pt i on
Use Legacy Treat ment The Use Legacy Tr eat ment opt ion is designed t o
keep compat ible wit h t he legacy BI P syst em. I n t his
model, all t he special t reat ment for BI P is exposed. But
t he t emperat ure dependent opt ion in t his model is
read- only which means user can only define t he
const ant BI P in t his model. Besides, t he BI P which is
special t reat ed can not be changed by user.
Use Flexible Treat ment The Use Fl ex i bl e Tr eat ment opt ion is designed t o
expose all t he special t reat ment for BI P in UniSim
Design and improve some pairs of BI P. I n t his model,
user can fully cont rol each BI P, such as enable or
disable a t emperat ure dependent BI P. And all t he BI P
in t he view will be t he exact ly one used in flash
calculat ion.
Fi gur e 2. 28
Bi nar y Coef f i ci ent s Tab
for more informat ion.
2- 41
b zero paramet er of t he ZJ equat ion t o be zero.
Chien Null
The Chien Null model provides a consist ent framework for applying
different act ivit y models on a binary by binary basis. On t he Paramet ers
t ab, you can specify t he Act ivit y Model t o be used for each component
pair, as well as t wo addit ional pure component paramet ers required by
t he model.
The t wo groups on t he Paramet er s t ab for t he Chien Null propert y
package are:
Chien Null Component Paramet ers
Chien Null Binary Component Paramet ers
Component Paramet ers
Values for t he Solubilit y and Molar Volume are displayed for each library
component and est imat ed for hypot het icals.
The Molar Volume paramet er is used by t he Regular Solut ion port ion of
t he Chien Null equat ion. The Regular Solut ion is an Act ivit y Model
choice for Binary pair comput at ions ( see t he following sect ion) .
Fi gur e 2. 29
Fi gur e 2. 30
2- 42
Binary Component Paramet ers
All of t he component s in t he case, including hypot het icals, are list ed in
t he mat rix. You can view t he det ails for t he liquid and vapour phase
calculat ions by select ing t he appropriat e radio but t on:
Liq Act ivit y Models
Vir ial Coefficient s
By select ing t he Liq Act ivit y Models radio but t on, you can specify t he
Act ivit y Model t hat UniSim Design uses for t he calculat ion of each
binary. The mat rix displays t he default propert y package met hod
select ed by UniSim Design for each binary pair.
The choices are accessed by highlight ing t he drop- down list in each cell.
I f Henry' s Law is applicable t o a component pair, UniSim Design select s
t his as t he default propert y met hod. When Henry' s Law is select ed by
UniSim Design, you cannot modify t he model for t he binary pair.
I n t he previous view, NRTL was select ed as t he default propert y
package for all binary pair s. You can use t he default select ions, or you
can set t he propert y package for each binary pair. Remember t hat t he
select ed met hod appears in bot h cells represent ing t he binary. UniSim
Design may filt er t he list of opt ions according t o t he component s
involved in t he binary pair.
By select ing t he Virial Coefficient s radio but t on, you can view and edit
t he virial coefficient s for each binary. Values are only shown in t his t able
when t he Virial Vapour model is select ed on t he Set Up t ab. You can use
t he default values suggest ed by UniSim Design or edit t hese values.
Virial coefficient s for t he pure species are shown along t he diagonal of
t he mat rix t able, while cross coefficient s, which are mixt ur e propert ies
bet ween component s, are t hose not along t he diagonal.
Wilson
The Molar Volume for each library component is displayed, as well as
Fi gur e 2. 31
The Propert y Packages
available in t he drop- down
list are:
None Required
Henry
van Laar
Margules
NRTL
Scat chard
Reg Soln
General
2- 43
t hose values est imat ed for hypot het icals.
Chao Seader & Grayson St reed
The Chao Seader and Grayson St reed models also use a Molar Volume
t erm. Values for Solubilit y, Molar Volume, and Acent ricit y are displayed
for library component s. The paramet ers are est imat ed for
hypot het icals.
Ant oine
UniSim Design uses a six t erm Ant oine expression, wit h a fixed F t erm.
For library component s, t he minimum and maximum t emperat ure and
t he coefficient s ( A t hrough F) are displayed for each component . The
Fi gur e 2. 32
Fi gur e 2. 33
2- 44
values for Hypot het ical component s are est imat ed.
2. 4. 3 Binary Coefficient s Tab
The Binary Coefficient s ( Binary Coeffs) t ab cont ains a mat r ix t able
which list s t he int eract ion paramet ers for each component pair.
Depending on t he propert y met hod select ed, different est imat ion
met hods may be available and a different view may be shown. You have
t he opt ion of overwr it ing any library value.
The cells wit h unknown int eract ion paramet ers cont ain dashes ( - - - ) .
When you exit t he Basis Manager, unknown int eract ion paramet ers are
set t o zero.
For all mat r ices on t he Binary Coeffs t ab, t he horizont al component s
across t he t op of t he mat rix t able represent t he " i" component and t he
vert ical component s represent t he " j " component .
Generalized Cubic Equat ion of St at e
I nt eract ion Paramet ers
When GCEOS is t he select ed propert y package on t he Set Up t ab, t he
Fi gur e 2. 34
Not e: The Bi nar y Coef f s t ab f or t he Gl y col Pr oper t y pack age
cont ai ns a page f or bot h EOS and Act i v i t y Model I nt er act i on
Par amet er s.
2- 45
Binary Coeffs t ab appears as shown below.
The GCEOS propert y package allows you t o select mixing met hods used
t o calculat e t he equat ion of st at e paramet er, a
ij
. UniSim Design
assumes t he - following general mixing rule:
where:
MR
ij
= t he mixing rule paramet er.
There are seven met hods t o choose for MR
ij
:
Fi gur e 2. 35
(2.27)
Equat i on
(2.28)
(2.29)
(2.30)
(2.31)
where:
(2.32)
a
ij
a
i
a
j
MR
ij
=
MR
ij
T ( ) 1 A
ij
B
ij
T C
ij
T
2
+ + ( ) =
MR
ij
T ( ) 1 A
ij
B
ij
T C
ij
T + + ( ) =
MR
ij
T ( ) 1 x
i
A
ij
B
ij
T C
ij
T
2
+ + ( ) x
j
A
ij
B
ij
T C
ij
T
2
+ + ( ) =
MR
ij
T ( ) 1 x
i
A
ij
B
ij
T C
ij
T + + ( ) x
j
A
ij
B
ij
T C
ij
T + + ( ) =
MR
ij
T ( ) 1
k
ij
k
ji
( )
x
i
k
ij
x
j
k
ji
+
------------------- =
k
ij
A
ij
B
ij
T C
ij
T
2
+ + =
2- 46
Each mixing rule allows for t he specificat ion of t hr ee paramet ers: A
ij
, B
ij

and C
ij
, except for t he Wong Sandler mixing rule which has t he A
ij
and
B
ij
paramet er and also requires you t o provide NRTL binary coefficient s.
The paramet ers are available t hrough t he t hree radio but t ons in t he
upper left corner of t he t ab: Aij , Bij and Cij / NRTL. By select ing a cert ain
paramet er s radio but t on you may view t he associat ed paramet er
mat rix t able.
Wong Sandler Mixing Rule
The Wong Sandler
1
mixing rule is a densit y independent mixing rule in
which t he equat ion of st at e paramet ers a
mix
and b
mix
of any cubic
equat ion of st at e are det ermined by simult aneously solving:
t he excess Helmholt z energy at infinit e pressure.
t he exact quadrat ic composit ion dependence of t he second virial
coefficient .
To demonst rat e t his model, consider t he relat ionship bet ween t he
second viral coefficient B( T) and t he equat ion of st at e paramet ers a and
b:
Consider t he quadrat ic composit ion dependence of t he second virial
where:
(2.33)
Wong Sandler Mixing Rule - Refer t o Wong Sandl er Mi x i ng Rul e
sect ion for more informat ion.
When sel ect i ng t he Ci j / NRTL r adi o but t on y ou ar e speci f y i ng
t he C
i j
par amet er unl ess y ou ar e usi ng t he Wong Sandl er
mi x i ng r ul e. I n t hi s case you ar e speci f yi ng NRTL bi nar y
coef f i ci ent s used t o cal cul at e t he Hel mhol t z ener gy.
(2.34)
Equat i on
MR
ij
T ( ) 1
k
ij
k
ji
( )
x
i
k
ij
x
j
k
ji
+
------------------- =
k
ij
A
ij
B
ij
T
C
ij
T
----- + + =
B T ( ) b
a
RT
----- =
2- 47
coefficient as:
Subst it ut e B wit h t he relat ionship in Equat i on ( 2. 34) :
To sat isfy t he requirement s of Equat i on ( 2. 36) , t he relat ionship for
a
mix
and b
mix
are:
wit h:
where:
F( x) = is an arbirt rary funct ion
The cross second virial coefficient of Equat i on ( 2. 9) can be relat ed t o
t hose of pur e component s by t he following relat ionship:
The Helmholt z fr ee energy depart ure funct ion is t he difference bet ween
t he molar Helmholt z free energy of pure species i and t he ideal gas at
const ant P and T.
(2.35)
(2.36)
(2.37)
(2.38)
(2.39)
(2.40)
B
m
T ( ) x
i
x
j
B
ij
T ( )
j
=
b
mix
a
mix
RT
------- x
i
x
j
b
a
RT
-----
\ .
| |
ij
j
=
b
mix
x
i
x
j
b
a
RT
-----
\ .
| |
ij
j
1
F x ( )
RT
--------
----------------------------------- =
a
mix
b
mix
F x ( ) =
b
a
RT
-----
\ .
| |
ij
b
i
a
i
RT
-----
\ .
| |
b
j
a
j
RT
-----
\ .
| |
+
2
--------------------------------------- 1 A
ij
B
ij
T ( ) =
A
i
T P , ( ) A
i
IG
T P , ( ) P v d
v =
v
i
}
\ .
|
|
| |
RT
v
----- v d
v =
RT
P
-----
}
\ .
|
|
|
| |
=
2- 48
The expression for A
e
is derived using lat t ice models and t herefore
assumes t hat t here are no free sit es on t he lat t ice. This assumpt ion can
be approximat ed t o t he assumpt ion t hat t here is no free volume. Thus
for t he equat ion of st at e:
b
mix
can be approximat ed by t he following:
t herefor e a
mix
is:
and F( x) is:
The Helmholt z free energy, , is calculat ed using t he NRTL model.
You are requir ed t o supply t he binary coefficient values on t he
paramet ers mat rix when t he Cij / NRTL radio but t on is select ed. Not e
t hat t he o t erm is equal t o 0. 3.
(2.41)
(2.42)
(2.43)
(2.44)
v
i
P
lim b
i
=
v
mix
P
lim b
mix
=
b
mix
x
i
x
j
b
a
RT
-----
\ .
| |
ij
j
1
A
e
x ( )
RT
-----------
\ .
|
| |
x
i
a
i
b
i
RT
--------
\ .
| |
i
+
------------------------------------------------ =
a
mix
b
mix
------- x
i
a
i
b
i
--- A
e
x ( )
i
=
F x ( ) x
i
a
i
b
i
--- A
e
x ( )
i
=
A
e
x ( )
2- 49
Equat ion of St at e I nt eract ion Paramet er
The Equat ion of St at e I nt eract ion Paramet ers group is shown below for
a select ed EOS pr opert y package as displayed on t he Binary Coeffs t ab
using an EOS, as displayed on t he Binary Coeffs t ab when an EOS is t he
select ed propert y package, is shown below.
The numbers displayed in t he t able are init ially calculat ed by UniSim
Design, but you can modify t hem. All known binary int eract ion
paramet ers are displayed, wit h unknowns displayed as dashes ( - - - ) .
You have t he opt ion of overwrit ing any library value.
For all Equat ion of St at e paramet ers ( except PRSV) , K
ij
= K
j i
, so when
you change t he value of one of t hese, bot h cells of t he pair
aut omat ically updat e wit h t he same value. I n many cases, t he library
int eract ion paramet ers for PRSV do have K
ij
= K
j i
, but UniSim Design
does not force t his if you modify one paramet er in a binary pair.
I f you are using PR ( Using Legacy Treat ment ) , SRK ( or one of t he Sour
opt ions) , PR-Twu, SRK-Twu or Twu- Sim-Tassone, t wo radio but t ons are
displayed at t he bot t om of t he t ab.
Fi gur e 2. 36
Est i mat e HC- HC/
Set Non HC- HC
t o 0. 0
This radio but t on is t he default select ion. UniSim
Design provides t he est imat es for t he int eract ion
paramet ers in t he t able, set t ing all nonhydrocarbon
pairs t o 0.
Set Al l t o 0. 0 When t his is select ed, UniSim Design set s all
int eract ion paramet er values in t he t able t o 0. 0.
This informat ion applies
t o t he following Propert y
Packages:
Kabadi Danner
Lee- Kesler Plocker
PRSV
PR Twu
Soave Redlich
Kwong, SRK
Sour PR
Sour SRK
SRK Twu
Zudkevit ch Joffee
Twu- Sim-Tassone
These t wo radio but t ons only appear
for t he PR and SRK based Equat ions
of St at e.
This is equivalent t o no K
ij
2- 50
Peng- Robinson I nt eract ion Paramet er
The view shown in t he Binary Coeffs t ab depends on t he user select ion
on t he BI P special t reat ment opt ion. By default , Use Legacy
Tr eat ment is select ed and t he int eract ion paramet ers for each binary
pair are displayed; unknown values for Aij , Bij , Cij will show as dashes
( - - - ) , and t he unknown values for Dij , Eij will show as EMPTY
( < empt y> ) .
Use Legacy Treat ment
When Peng- Robinson is t he select ed propert y package on t he Set Up
t ab and t he "Use Legacy Tr eat ment " is chosen as t he BI P special
t reat ment met hod, t he Binary Coeffs t ab appears as shown below.
I n Use Legacy Tr eat ment model, all t he special t reat ment for BI P is
exposed as black color and can not be specified by user, such as t he
t emperat ure dependent BI P bet ween H2O/ H2S, et c. Moreover, for ot her
ordinary const ant BI P, Aij is t he only one coefficient which is adj ust able
and Bij , Cij , Dij , Eij as well as t he t emperat ure dependent opt ion are all
read- only. I t means user can only define t he const ant BI P in Use
Legacy Tr eat ment model.
Use Flexible Treat ment
Use Flexible Treat ment model is designed t o make t he BI P t emperat ur e
dependent and ensure all t he BI P coefficient s can be specified by user.
Besides, t he est imat ion of t he BI P for component s likes CO2 & H2S wit h
hydrocarbons ( C10 < C < C20) and hypo component s are improved in
Fi gur e 2. 37
Par amet er s Tab for
more informat ion.
2- 51
t his model.
When Use Fl ex i bl e Tr eat ment is chosen as t he BI P special t reat ment
met hod, t he Binary Coeffs t ab appears as shown below.
And t he t emperat ure dependent opt ion can be showed if t he BI P opt ion
is chosen. I f user decides t o make t he BI P pair t o be t emperat ure
dependent , t he checkbox should be checked first ly.
The t emperat ure dependent form is fixed as:
The correlat ion for t he est imat ion of t he BI P for component s likes CO2
Fi gur e 2. 38
Fi gur e 2. 39
(2.45)
) / (
2
T E D Exp T C T B A k
ij ij ij ij ij ij
+ + + + =
2- 52
& H2S wit h hydrocarbons ( C10 < C < C20) and hypo component is:
where:
MW ( i) = molecular weight of t he hydrocarbons or hypo component
Max i mum Est i mat ed BI P f or HC box: The maximum value allowed
for BI P ofhydrocarbon compounds during package init ializat ion. I t is not
used unless a value is specified by t he user. The Check Upper Li mi t
but t on will clamp HC- HC BI P values t o a upper limit ed defined by t he
ent ry in t he Maximum Est imat ed BI P for HC field.
Act ivit y Model I nt eract ion Paramet ers
The Act ivit y Model I nt eract ion Paramet ers group, as displayed on t he
Binary Coeffs t ab when an Act ivit y Model is t he select ed propert y
package, is shown in t he figure below.
The int eract ion paramet ers for each binary pair ar e displayed; unknown
values will show as dashes ( - - - ) . You can over writ e any value or use
one of t he est imat ion met hods. The est imat ion met hods are described
in t he following sect ion.
To display a different coefficient mat rix ( i. e., B
ij
) , select t he appropriat e
radio but t on.
(2.46)
Fi gur e 2. 40
0928 . 0 ) ( * 005 . 0 + = i MW k
ij
Only available wit h PR
EOS.
There is no Tr eat ment
of I nt er act i on
Coef f i ci ent s
Unav ai l abl e f r om
Li br ar y and Max i mum
Est i mat ed BI P f or HC
opt ion for Use Fl ex i bl e
Tr eat ment model.
t o t he following
propert y packages:
Chien Null
Ext ended NRTL
General NRTL
Margules
NRTL
UNI QUAC
van Laar
Wilson
The numbering and naming of t he radio but t ons select ions
vary according t o t he select ed Act ivit y Model.
You may reset t he
binary paramet ers t o
t heir original library
values by clicking t he
Reset Params but t on.
2- 53
Est imat ion Met hods
When using Act ivit y Models, UniSim Design provides t hree int eract ion
paramet er est imat ion met hods. Select t he est imat ion met hod by
select ing one of t he following radio but t ons and t hen invoke t he
est imat ion by select ing one of t he available but t ons:
I f you have select ed eit her t he UNI FAC VLE or UNI FAC LLE est imat ion
met hod, you can apply it in one of t he following ways, by select ing t he
appropriat e but t on:
UNI FAC
VLE
UniSim Design calculat es paramet ers using t he UNI FAC VLE
model.
UNI FAC
LLE
UniSim Design calculat es all paramet ers using t he UNI FAC
LLE model.
I mmi sci bl e The t hree but t ons used for t he UNI FAC est imat ions are
replaced by t he following:
Row i n Cl m Pai r. Use t his but t on t o est imat e t he
paramet ers such t hat t he row component ( j ) is
immiscible in t he column component ( i) .
Cl m i n Row Pai r. Use t his but t on t o est imat e
paramet ers such t hat t he column component s ( j ) are
immiscible in t he row component s ( i) .
Al l i n Row . Use t his but t on t o est imat e paramet ers
such t hat bot h component s are mut ually immiscible.
Si nce t he Wi l son equat i on does not handl e t hr ee phase
sy st ems, t he Coef f Est i mat i on gr oup does not show t he
UNI FAC LLE or I mmi sci bl e r adi o but t ons w hen t hi s pr oper t y
pack age i s used.
I ndi v i dual
Pai r
This but t on is only visible when UNI FAC VLE is select ed. I t
calculat es t he paramet ers for t he select ed component pair,
Aij and Aj i. The exist ing values in t he mat rix are
overwrit t en.
Unk now ns
Onl y
I f you delet e t he cont ent s of cells or if UniSim Design does
not provide default s values, you can use t his opt ion and
have UniSim Design calculat e t he act ivit y paramet ers for all
t he unknown pairs.
Al l Bi nar i es Recalculat es all t he binaries in t he mat rix. I f you had
changed some of t he original UniSim Design values, you
can use t his t o have UniSim Design re- est imat e t he ent ire
mat rix.
Alphaij = Alphaj i, but
Aij Aj i. =
UNI FAC est imat ions are
by default performed at
25C, unless you change
t his value on t he Set Up
t ab.
You may reset t he
binary paramet ers t o
t heir original library
values by clicking t he
Reset Params but t on.
2- 54
2. 4. 4 St abilit y Test Tab
The st abilit y t est can be t hought of as int roducing a " droplet " of nucleus
int o t he fluid. The droplet t hen eit her grows int o a dist inct ive phase or
is dissolved in t he fluid.
For mult i- phase fluids, t here exist mult iple false calculat ed solut ions. A
false solut ion exist s when convergence occur s for a lower number of
phases t han exist s in t he fluid. For example, wit h a t hree- phase fluid,
t here is t he correct t hree- phase solut ion, at least t hree false t wo- phase
solut ions and mult iple false single- phase solut ions. A maj or problem in
converging t he flash calculat ion is arriving at t he right solut ion wit hout
a pr ior knowledge of t he number of equilibrium phases.
The St abilit y Test allows you t o inst ruct UniSim Design on how t o
perform phase st abilit y calculat ions in t he Flowsheet . I f you encount er
sit uat ions where a flash calculat ion fails or you are suspicious about
result s, you can use t his opt ion t o approach t he solut ion using a
different rout e.
The st rat egy used in UniSim Design is as follows: unless t here is st rong
evidence for t hree phases, UniSim Design first performs a t wo- phase
flash. The result ing phases are t hen t est ed for t heir st abilit y.
Fi gur e 2. 41
2- 55
Flash Algorit hm Opt ions
Fl ash Opt i on Descr i pt i on
Tr y I OFl ash
f i r st
This act ivat es an alt ernat ive opt imized I nside- Out flash
algorit hm t hat may provide a significant speed
improvement in many cases. I t is aimed at dynamics
mode, but operat es in st eady st at e mode as well. The flash
can handle rigorous t hree phase calculat ions using t he
St abilit y Test Paramet ers set t ings, alt hough it is not t est ed
as well as t he default flash algorit hms and does not work
wit h all propert y packages. I f you experience problems
t hat are flash relat ed, t ry select ing or deselect ing t he
opt ion. For maximum speed in t wo phase syst ems, you can
also set t he Maximum Phases Allowed for t he fluid package
t o t wo in t he St abilit y Test Paramet ers group, or set t he
Met hod t o none t o disable t he t est .
Reduce St ep
Si ze
This checkbox will be act ive if user select s t he Mult iPhase
checkbox in Dynami cs Mode Secant Fl ash Opt i ons. I t
int roduces a maximum damping fact or for t he PT flash
algorit hm when t he default st rat egy fails t o converge. I t
can improve t he flash convergence, but not guarant ee t o
converge in all condit ions. This opt ion is only
recommended for user t o t ry when flash convergence
behavior oscillat es, such as vapour phase fract ion does not
increase monot onically on t emperat ure, and user really
cares about t he oscillat ions. I t is especially recommended
for t he difficult syst ems, like t hat happens in Urea process.
This opt ion will lead t o addit ional flash it erat ions and hence
can affect t he speed of t he simulat ion.
Cal c Accur at e
Zer o Phase
Composi t i ons
This act ivat es an alt ernat ive opt imized I nside- Out flash
algorit hm t hat may slow down t he simulat ion speed. I t is
aimed at dynamics mode, but operat es in st eady st at e
mode as well. The flash can handle rigorous t hree phase
calculat ions using t he St abilit y Test Paramet ers set t ings,
alt hough it is not t est ed as well as t he default flash
algorit hms and does not work wit h all propert y packages.
I f you experience problems t hat are flash relat ed, t ry
select ing or deselect ing t he opt ion. For maximum speed in
t wo phase syst ems, you can also set t he Maximum Phases
Allowed for t he fluid package t o t wo in t he St abilit y Test
Paramet ers group, or set t he Met hod t o none t o disable t he
t est .

2- 56
Dynamic Mode Secant Flash Opt ions
UniSim Design enables you t o modify t he flash calculat ion met hods t o
be used in Dynamics mode. There are t hree set t ing opt ions available:
I f t he I OFlash opt ion is select ed, t he Pressure Flow Solver group on t he
Dynamics page of t he Preferences opt ions allows t he flash t o be solved
simult aneously wit h heat t ransfer equat ions. The opt ion can result in a
furt her significant speed increase, but should only be used if t he case is
st able using I OFlash.
I f a dynamics case has more t han one liquid phase ( or if a single liquid
phase is aqueous or a hydrocarbon) , it is recommended t hat you use
t he Phase Sort ing Met hod for t he fluid package on t he Sect i on 2.4.5 -
Phase Or der Tab. By default , phases ar e sort ed on densit y and phase
t ypes. I f t he phase t ype changes, inst abilit ies may result . The Phase
Sort ing Met hods allow you t o clearly define t he order in which phases
should be defined so t hat t hey are consist ent .
St abilit y Test Paramet ers Group
You can specify t he maximum number of phases allowed ( 2 or 3) in t he
Maximum Phases Allowed input cell. I f t his value is set t o 2, t he st abilit y
t est quit s aft er 2- phase flashes. Occasionally, you may st ill get 3
phases, as t he flash may at t empt t o st art direct ly wit h t he 3- phase
flash.
The St abilit y scheme used is t hat proposed by Michelson. I n t he Met hod
group, you can select t he met hod for performing t he st abilit y t est
Fl ash Opt i on Descr i pt i on
Fl ash3 This is t he default secant flash algorit hm used in dynamics
mode. I t is fast , but does not perform rigorous phase
st abilit y t est s based on t he opt ion set in t he St abilit y Test
Paramet ers group. Hence, it may not always det ect a
second liquid phase when it is present .
Mul t i Phase This is a secant flash algorit hm t hat performs phase
st abilit y t est ing according t o t he set t ings in t he St abilit y
Test Paramet ers group. This opt ion is t ypically slower t han
t he flash3 opt ion. I t can be used when mult iple liquid
phases are import ant or in rare cases where using t he
flash3 opt ion result s in inst abilit ies due t o t he second liquid
phase not being det ect ed consist ent ly.
Use Mul t i
Phase
Est i mat es
The checkbox becomes available when you select Mult i
Phase as t he Secant Flash Opt ion. I f t he case consist s of
t hree phases, est imat es are passed t o t he flash which
speeds up some flashes.
I f t he I OFlash fails,
UniSim Design will
immediat ely go t o met hod
select ed in t he Secant
Flash Opt ions group.

UniSim Thermo is not
opt imized for dynamics
mode and may result in
performance issues if
used in dynamics mode.
2- 57
calculat ions by select ing one of t he following radio but t ons:
Phases t o I nit iat e Test
There are four choices list ed wit hin t he Phase( s) t o I nit iat e Test group.
These checkboxes are act ivat ed according t o t he radio but t on select ion
in t he Met hod group. I f you change t he st at us of any opt ion, t he radio
but t on in t he Met hod gr oup is aut omat ically set t o User.
I f any one of t hese init iat ing nuclei ( init ial guesses) forms a dist inct ive
phase, t he exist ing fluid is unst able and t his nucleus provides t he init ial
guess for t he t hree- phase flash. I f none of t hese init ial guesses shows
addit ional phases, it can only be said t hat t he fluid is likely t o be st able.
One limit at ion wit h t he st abilit y t est is t he fact t hat it relies on t he
propert y package chosen rat her t han physical realit y. At best , it is as
accurat e as t he propert y package. For inst ance, t he NRTL package is
None No st abilit y t est is performed.
Low Uses a default set of Phases/ Component s t o I nit iat e t he
St abilit y Test . This met hod includes t he Delet ed phases ( if
t hey exist ) , t he Wilson' s Equat ion init ial guess and t he
Wat er component ( if it exist s) in t he fluid.
Medi um I n addit ion t o t he opt ions used for t he Low met hod, t his
met hod also includes t he Average of Exist ing phase, t he
I deal Gas phase and t he heaviest and light est component s
in t he fluid.
Al l All available Phases and Component s are used t o init iat e
t he t est .
User Allows you t o act ivat e any combinat ion of checkboxes in
t he Phase( s) t o I nit iat e Test and Comp( s) t o I nit iat e Test
groups. I f you make changes when a default Met hod radio
but t on ( i. e., Low, Medium) is select ed, t he met hod will be
changed t o User aut omat ically.
Legacy
HYSI M Fl ash
This is t he flash met hod used in Legacy HYSI M. I f t his
choice is select ed, UniSim Design will use t he same flash
rout ines as in Legacy HYSI M and no st abilit y t est will be
performed. This opt ion allows comparison of result s
bet ween Legacy HYSI M and UniSim Design. This st abilit y
opt ion is not recommended for dynamics mode. Use t he
default flash3 opt ion wit h t he st abilit y paramet er set t o
none.
Check box es Descr i pt i on
Del et ed I f a phase is removed during t he 2- phase flash, a droplet of
t he delet ed fluid is re- int roduced.
Av er age of
Ex i st i ng
The exist ing equilibrium fluids are mixed in equal port ions;
a droplet of t hat fluid is int roduced.
I deal Gas A small amount of ideal gas is int roduced.
Wi l son' s
Equat i on
A hypot het ical fluid is creat ed using t he Wilson' s K-value
and is used t o init iat e t he st abilit y t est .
2- 58
known t o be ill- behaved in t he sense t hat it could act ually predict
numerous equilibrium phases t hat do not exist in realit y. Thus, t urning
on all init ial guesses for NRTL may not be a good idea.
Temperat ure Limit s
The t emperat ure limit s ar e int ended t o be used in dynamics mode and
are set t o st op t he flash when t he limit s are at t ained. I f t he limit s are
reached, t hen dynamics will ext rapolat e t hereaft er. The limit s avoid
pot ent ial problems wit h some propert y packages at low t emperat ures
and during severe process upset s where you would get numerical errors
and heat exchanger convergence problems.
Secant Flash Tolerances
The t olerances used in t he secant flash calculat ions are exposed t o give
t he user great er cont rol on t he convergence accuracy of t he flash
calculat ions. The default t olerances are shown in red. The user can
choose t o eit her t ight en or loosen t he t olerances t o suit his/ her needs.
Tight ening t he t olerances will result is t ight er convergence of t he flash
calculat ions but will lead t o more t hermodynamic comput at ions and
hence can affect t he speed of t he simulat ion. On t he ot her hand
loosening t he t olerances will r esult in fewer t hermodynamic
comput at ions but will compromise on t he convergence accuracy of t he
flash calculat ions. The Vapour Fract ion Tolerance is applied t o Pressure-
Vapour Fract ion and Temperat ure- Vapour Fract ion flashes. The
Ent halpy Tolerance is applied t o Pressur e- Ent halpy and Temperat ure-
Ent halpy flashes and t he Ent ropy Tolerance is applied t o Pressure-
Ent ropy and Temperat ure- Ent ropy flashes.
Component s t o I nit iat e Test
When a " droplet " of nucleus is int roduced int o t he fluid, t he dr oplet
eit her grows int o a dist inct ive phase or is dissolved in t he fluid. Anot her
obvious choice for t he droplet composit ion is one of t he exist ing pure
component s. For example, if t he fluid cont ains hexane, met hanol and
wat er, one could t ry int roducing a droplet of hexane, a droplet of
met hanol or a droplet of wat er. The choices for t he pure component
"droplet s" are list ed in t he Comp( s) t o I nit iat e Test group.
2. 4. 5 Phase Order Tab
The Phase order feat ure is int ended for dynamics. UniSim Design
2- 59
dynamics always uses t hree phases for st reams and fluids in t he st ream
propert y view. For each unit operat ion, dynamics also assumes t hat t he
same mat erial is in t he same phase slot for all of t he connect ed
st reams. The order of t he first phase is always vapour and t he second
phase is liquid. The t hird phase may be aqueous or it can be a second
liquid phase.
By default , UniSim Design sort s t hese phases based on t heir Type
( liquid or aqueous) and Phase Densit y. However, subt le changes t o t he
st ream propert ies may change t he order. St ream propert ies displayed
as a liquid phase in one inst ance may be displayed as an aqueous
phase in anot her. For example, inside a t ray sect ion t he composit ion of
a phase may change so t hat inst ead of being aqueous it is a liquid
phase. The phase moves t o a different slot in t he fluid. This can cause
dist urbances in dynamics mode.
Mat er i al St r eam
Pr oper t y Vi ew of t he
Uni Si m Desi gn
st ream propert ies.
2- 60
The Phase Sort ing Met hod includes t wo opt ions and is shown below.
Use Phase Type and Densit y
This opt ion can cause inst abilit ies in dynamics. I n pract ice if small
spikes are ident ified and an examinat ion of t he flowsheet r eveals t hat
some mat erial appears in different phase slot s in different part s of t he
flowsheet ( where t he spikes originat e) t han t he user specified opt ion is
recommended.
Use User Specified Primary Component s
The Use User Specified Primary Component s opt ion displays t he Select
Primary Phase Component s group t hat allows you t o specify which
component s should be in phase slot 1 and which component s should be
in phase slot 2. These checks are used t o det ermine t he phase order
wherever t he fluid package in quest ion is used.
I f t here is only one non- vapour phase present and t he mole fract ions of
t he primary component adds up t o more t han t he specified t hreshold, it
is considered t o belong in phase slot 1 and of t ype liquid 1. Ot herwise
t he rat io of primary component for t he t wo choices is examined.
This opt ion is recommended when:
a simulat ion is performed and it has more t han one liquid phase.
t he densit ies of t he t wo liquid phases may be close.
one or mor e phases is close t o being labelled eit her aqueous or
liquid.
Fi gur e 2. 42
This opt ion changes t he
order of phases in st eady
st at e as well. Alt hough in
st eady st at e many of t he
calculat ions depend on
t he phase t ype and not
t he order, and hence
should not have any
significant impact .
Changing t his opt ion
does not resolve t he
case or immediat ely
updat e t he affect ed
st reams. The changes
occur while t he
int egrat or is running,
which minimizes
dist urbances.
2- 61
Solids Merge Opt ion
This opt ion only needs t o be considered if you have solid component s in
t he Component List associat ed wit h t his Fluid Package.
I n UniSim Design Dynamics, a Fluid ( which is part of t he st ream as well
as in unit operat ions) will always have 3 Phases. This is in cont rast t o
st eady st at e mode where, if you view t he Worksheet t ab, Condit ions
page of a st ream and st ret ch it wider, you may see t he number of
phases changing depending on t he solut ion in st eady st at e - if any
phase has zero phase fract ion as predict ed by t he flash, t hen t hat
phase does not even show. You may see 4 phases - vapour, liquid 1,
liquid 2 ( or aqueous) and solid.
Due t o t he fact t hat dynamics was only designed for 3 phases, a
merging of t wo ( non- vapour) phases must be done. This merging is
done by a simple mole fract ion weight ing of t he relevant propert ies.
This will ensure a component and energy balance.
The user has 3 choices wit h which t o collapse t he 3 phases int o 2. By
using t he first opt ion of Merge Liquid 2 int o Liquid 1, t he fluid will
always be assured of having a dist inct and pure solid phase if t here is
non- zero overall mole fract ion of solid in t he fluid. This is t he
suggest ed opt ion when modelling solids since t he user likely want s t o
see a pure solid phase which can be measured - if t wo liquid phases
exist , t hese will be merged as one.
Anot her opt ion det ermines if t he merging is always done, even wit h
zero phase fract ion phases. This is best described by an example when
using t he Merge Liquid 2 int o Liquid 1. I f t his Always Merge checkbox is
off and a flowing st ream has solids in it ( non- zero) , t hen one will see a
Vapour, Liquid and Solid phase. However, if t he upst ream operat ions
change such t hat t he solids overall mole fract ion dr ops t o zero, t hen t he
Solid phase in t he st ream will disappear and will be replaced by a
second Liquid ( perhaps Aqueous) phase. Wit h t he Always Merge
checkbox on, t he Solid phase does not disappear but inst ead j ust shows
zero phase fract ion and t he t wo liquid phases are always mer ged.
The benefit of t he Always Merge opt ion is t hat t he dynamic model will
be more accurat e and in fact more st able. Tur ni ng t hi s on i s t he
r ecommended opt i on. This is because t he dynamic flash calculat ions
rely on mixing phases from t he same phase slot and if t he mat er ial in a
part icular phase slot may change dynamically, t he appr oximat e flash
and ot her blending calculat ions are not correct . This is part icularly t rue
if you are using non- 100% dynamic efficiencies. To see t he benefit of
t he Always Merge opt ion, t ry creat ing a model which has t wo feeds int o
a mixer. The first feed which is flowing should have component s t o
2- 62
produce wat er, hydrocarbon and solid phases. The second feed which t o
st ar t wit h has zero flow, should be pure wat er. Now wit h t he Merge
Liquid 2 int o Liquid 1 opt ion and t he Always Merge disabled, t ry
t ransit ioning t o st op t he flow from t he first feed and st ar t t he flow from
t he second. You will see t hat t he mixer operat ion is not correct in it s
predict ion of out let phase fract ions and composit ions. However wit h
t he Always Merge opt ion t urned on, t his simulat ion is correct . Not e t hat
you should perform t his t est wit h t he default Composit ion frequency of
10 - if you use a composit ion frequency of 1, t he problem is
significant ly reduced.
The downside of using t he Always Merge opt ion is t hat t he modeller has
t o decide where t o use a fluid package wit h t his on and where t hey
might need t o add a st ream cut t er and t ransit ion t o a fluid package
wit hout any merging. Consider as an example a Fluidized Cat alyt ic
Cracking unit common wit hin refineries. I n t he r eact or, riser and
cyclones t here is some solid cat alyst and coke. Some small amount of
t his is carried wit h t he overhead vapour our of t he cyclone sect ion int o
t he bot t om of t he Main Fract ionat or. From t here any solid is carried
wit h t he bot t oms liquid t hrough a pump t ypically recycled back t o t he
recycle sect ion. To model t his, a fluid package wit h solids should be
used for t he react or and Main Frac bot t oms sump. The Always Merge
opt ion should be t urned on and t he user can decide if t hey want Solids
Merged int o Liquid2 or some ot her merge opt ion. For t he Main Frac
above t he bot t om sump, however, St ream Cut t ers should be added and
a new fluid package should be used wit h t he No Merge opt ion or
preferably wit hout even t he solid component present in t hat component
list .
2. 4. 6 React ions Tab
Wit hin t he Basis Environment , all react ions are defined t hrough t he
React ion Manager ( React ions t ab of t he Simulat ion Basis Manager) . On
t he Rxns t ab of t he Fluid Package propert y view, you are limit ed t o
See Chapt er 5 -
React i ons for more
informat ion.
2- 63
at t aching/ det aching react ion set s.
The obj ect s for t he Rxns t ab wit hin t he Fluid Package propert y view are
described below.
2. 4. 7 Tabular Tab
The Tabular Package can regress t he experiment al dat a for select
t hermophysical proper t ies such t hat a fit is obt ained for a chosen
mat hemat ical expression. The Tabular Package is ut ilized in conj unct ion
wit h one of t he UniSim Design propert y met hods. Your t ar get ed
propert ies are t hen calculat ed as replacement s for what ever procedure
t he associat ed propert y met hod would have used.
Alt hough t he Tabular Package can be used for calculat ing every
propert y for all component s in t he case, it is best used for mat ching a
specific aspect of your process. A t ypical example would be in t he
Fi gur e 2. 43
Cur r ent
React i ons Set s
This list s all t he current ly loaded react ions set in t his
Fluid Package.
Associ at ed
React i ons
There are t wo Associat ed React ions list boxes. Bot h
boxes displays all t he react ions associat ed wit h t he
respect ive select ed React ion Set .
Add Set This but t on at t aches t he highlight ed Available React ion
Set t o t he Fluid Package and displays it in t he Current
React ions Set s group.
Remov e This but t on removes t he highlight ed Current React ion
Set from t he Fluid Package.
Av ai l abl e
React i ons Set s
This list - box displays all t he Available React ions Set s in
t he case.
Si mul t aneous
Basi s Mgr
Click t his but t on t o access t he React ion Manager.
2- 64
calculat ion of viscosit ies for chemical syst ems, where t he Tabular
Package will oft en provide bet t er result s t han t he Act ivit y Models.
Tabular Package calculat ions are based on mat hemat ical expressions
t hat represent t he pure component propert y as a funct ion of
t emperat ure. The values of t he propert y for each component at t he
process t emperat ure are t hen combined, using t he st ream composit ion
and mixing rule t hat you specify.
The Tabular provides access t o a comprehensive regression package.
This allows you t o supply experiment al dat a for your component s and
have UniSim Design regress t he dat a t o a select ed expression.
Essent ially, an unlimit ed number of expressions are available t o
represent your propert y dat a. There are 32 basic equat ion shapes, 32 Y
t erm shapes, 29 X t er m shapes, as well as Y and X power funct ions. The
Tabular provides plot t ing capabilit ies t o examine how well t he select ed
expression predict s t he propert y. You are not r est rict ed t o t he use of a
single expression for each propert y. Each component can be
represent ed using t he best expression.
You may not need t o supply experiment al dat a t o use t he Tabular. I f you
have access t o a mat hemat ical represent at ion for a component /
propert y pair, you can simply select t he correct equat ion shape and
supply t he coefficient s direct ly. Furt her, UniSim Design provides a dat a
base for nearly 1, 000 library component s, so you can use t his
informat ion direct ly wit hin t he Tabular wit hout supplying any dat a
what soever.
I n addit ion, UniSim Design can direct ly access t he informat ion in t he
PPDS dat abase for use in t he Tabular. This dat abase is similar t o t hat
provided wit h UniSim Design in t hat t he pr opert ies for t he component s
are represent ed using a mat hemat ical expression.
UniSim Design can now also direct ly access t he propert y curve
informat ion for Viscosit y ( Vapor and Liquid) , Thermal Conduct ivit y
( Vapor and Liquid) , Densit y ( Liquid) and Surface Tension using a
component dat abase such as DI PPR t hrough t he Component Curve
Opt ion ( Use CCO) . The dat abase is similar t o t hat provided wit h UniSim
Design in t hat t he propert ies for t he component s are represent ed by
UniSim Design cont ains
a default library
cont aining dat a for over
1,000 component s.
Whenever experiment al
dat a is supplied, it is
ret ained in t he memory
by UniSim Design and
st ored in t he case.
The PPDS dat abase is an
opt ional t abular feat ure.
Cont act your Honeywell
for furt her informat ion.
The CCO is an opt ional
t abular feat ure. Cont act
your Honeywell for
furt her informat ion.
2- 65
using a mat hemat ical expression
Requirement s for Using t he Tabular
There ar e only t wo requirement s on t he usage of t he Tabular package.
First , most propert ies require t hat all component s in t he case have t heir
propert y value calculat ed by t he Tabular. Second, ent halpy calculat ions
require t hat t he Tabular be used for bot h t he liquid and vapour phase
calculat ions. Similarly, you may use only one ent halpy t ype propert y for
each phase. For example, liquid ent halpy and liquid heat capacit y
cannot bot h be select ed. An ext ension t o t his occurs when t he lat ent
heat propert y is select ed. When t his propert y is act ivat ed, only one
ent halpy t ype propert y or one heat capacit y propert y may be select ed.
Limit s in t he Tabular Opt ion
I n ent halpy ext rapolat ion, if t he upper t emperat ure limit ( T
max
) is less
t han t he crit ical t emperat ure ( T
c
) UniSim Design Tabular opt ion
cont inues t o ext rapolat e t he dat a based on t he or iginal curve up t o t he
crit ical point . At t his point , an int ernal ext rapolat ion met hod is used t o
calculat e t he liquid ent halpy. Due t o t he int ernal ext rapolat ion met hod,
t here may be a huge discont inuit y and poor ext rapolat ion result s from
T
max
t o T
c
. The poor calculat ed values cause pr oblem wit h t he PH flash
calculat ion.
There are t wo met hods t o avoid t his problem:
I ncrease t he T
max
value of t he or iginal ent halpy curve. However,
as ment ioned above t he cur ve it self does not ext end above T
max

very well and produces poor result s. You will have t o be
responsible for changing t he curve shape t o ext rapolat e in a
bet t er manner.
The Heat of Mi x i ng pr oper t y can be appl i ed i n one of t w o
manner s. For Act i v i t y Model s t hat do not have Heat of Mi x i ng
cal cul at i ons bui l t i n, t hi s al l ow s you t o suppl y dat a or have
t he coef f i ci ent s est i mat ed, and have Heat s of Mi x i ng appl i ed
t hr oughout t he f l ow sheet . Equat i ons of St at e do account f or
Heat of Mi x i ng i n t hei r ent hal py cal cul at i ons, how ever , i n
cer t ai n i nst ances pr edi ct t he val ue i ncor r ect l y. You can use
t hi s r out e t o appl y a cor r ect i on f act or t o t he Equat i on of
St at e.
I n t he cases w her e t he Equat i on of St at e i s pr edi ct i ng t oo
hi gh a val ue, i mpl ement i ng a negat i ve Heat of Mi x i ng can
cor r ect t hi s.
2- 66
User t he Ent halpy Model T
r
Limit opt ion. This opt ion allows you
t o cont rol t he st art ing t emperat ure at which t he ext rapolat ion
met hod is implement ed. So inst ead of T
c
, t he ext rapolat ion will
st ar t at a cert ain T
r
( t he default value is 0, which t ells UniSim
Design t o use t he default met hod) t ypically 0. 7 t o 0. 99.
Ext rapolat ing accurat e/ adequat e dat a is import ant , especially for
ent halpy values approaching t he crit ical point , as t he values can change
in odd manner and may requir e special ext rapolat ion.
I f you are not using PPDS mixing rules ( PPDS ext rapolat ion met hods)
UniSim Design supplies a very simple ext rapolat ion based on const ant
C
p
calculat ed from t he or iginal t abular ent halpy cur ve. This met hod
keeps everyt hing monot onically increasing t hrough t he crit ical point
and int o t he dense phase.
Using t he Tabular Package
When using t he Tabular package a general sequence of st eps is shown
below:
1. Enable t he Opt ions, Conf i gur at i on and Not es pages by checking
t he Enabl e Tabul ar Pr oper t i es checkbox.
2. Select t he Basi s f or Tabul ar Ent hal py by clicking t he appropriat e
radio but t on on t he Conf i gur at i on page.
Fi gur e 2. 44
2- 67
3. Select t he checkboxes for t he desired t arget propert ies from t he All
Propert ies, Physical and Thermodynamic pages in t he Opt ions t ree
configurat ion. The Al l Pr oper t i es page is shown below.
As propert ies are added, t he I nformat ion t r ee also becomes
expandible. This may be done by clicking on t he + t hat appears in
fr ont of t he I nformat ion label. Expanding t his t ree displays all of t he
act ive t arget propert ies select ed on t he Opt ions pages. I f t he Heat
of Mixing proper t y is act ivat ed on t he All Proper t ies or
Thermodynamics page, a new expandible t ree for Heat of Mixing
appears in t he Tabular Package group.
4. I f you have t he PPDS dat abase, click t he checkbox for t he dat abase.
5. I f a component dat abase such as DI PPR is available and being used,
click t he checkbox under t he Use CCO column for t he specific
propert y. I f t he component cont ains t he propert y curves, t he
values will be t ransferred t o Tabular and used ot herwise t he
propert y cur ve values will be est imat ed. A message in t he t race
window will be displayed aft er each component propert y is
est imat ed. I f component propert y curve values are subsequent ly
changed t hey will not be aut omat ically t ransferred t o Tabular. I f t he
user needs t o affect t his t ransfer t he specific propert y will need t o
be unchecked and re- checked.
6. Once a t arget propert y is select ed on one of t he t hree Opt ions
pages, you may select t he Mi x i ng Basi s by using t he drop- down
list . The Paramet er value may also be changed on t his page.
Fi gur e 2. 45
To view all pages under
t he opt ions, use t he +
t o expand t he t ree.
2- 68
7. To view t he exist ing library informat ion, you must first select t he
desired page from t he expandible I nformat ion t ree. Click t he desired
propert y from t he t r ee list .
8. To plot t he exist ing library informat ion, click t he Cmp Pl ot s but t on.
Click a component using t he drop- down list in t he Curve Select ion
group t o change t he component s being plot t ed. The variables,
Ent halpy vs. Temperat ur e are plot t ed from t he Variables gr oup and
shown in t he figure below.
Fi gur e 2. 46
Fi gur e 2. 47
2- 69
9. Ret urn t o t he I nf or mat i on page of t he propert y by closing t he plot
view. To view t he PropCur ve pr opert y view for a select ed
component , highlight a value in t he column of t he desired
component and click t he Cmp Pr op Det ai l but t on.
10. Set t he Equat ion Form and supply dat a. You can view t his same
format of dat a for library component s.
The Tabular t ab of t he fluid package propert y view cont ains t wo pages
and t hree t rees of informat ion, which are displayed at different t imes
depending on t he opt ions select ed. These pages are:
Configurat ion Page
Opt ions Tree
I nformat ion Tree
Heat of Mixing Tree ( appears only when Heat of Mixing is
act ivat ed in t he Opt ions)
Not es
Configurat ion Page
The configurat ion page consist s of t wo gr oups, t he Global Tabular
Fi gur e 2. 48
2- 70
Calculat ion Opt ions, and t he Basis for Tab. Ent halpy ( ideal gas) .
Global Tabular Calculat ion Behaviour Group
The Global Tabular Calculat ion Behaviour Group cont ains t wo checkbox
opt ions:
Fi gur e 2. 49
Check box Descr i pt i on
Enabl e
Cal cul at i on
of Act i v e
Pr oper t i es
I f t his is act ivat ed, all t he select ed Act ive Propert ies are
calculat ed via t he Tabular Package. I f t his checkbox is not
act ivat ed, all propert ies are calculat ed by t he Propert y
Package. This provides a mast er swit ch t o enable/ disable
t he Tabular Package while ret aining t he Act ive Propert y
select ions.
Enabl e
Tabul ar
Pr oper t i es
Toggles t he Tabular Propert ies on or off. I f t he checkbox is
t oggled off, no ot her pages are available and none of t he
previously input t ed dat a is st ored.
The di f f er ence bet w een t he Enabl e Cal cul at i on of Act i ve
Pr oper t i es and t he Enabl e Tabul ar Pr oper t i es check box es:
The Enabl e Cal cul at i on of Act i v e Pr oper t i es check box t oggl es
bet w een t he pr oper t i es r egr essed f r om t he dat a suppl i ed on
t he Tabul ar t ab and t he def aul t val ues cal cul at ed by t he
Pr oper t y Pack age. Whi l e deact i vat i ng t he check box r et ur ns
t o t he def aul t Pr oper t y Pack age val ues, t he t ab r et ai ns al l
i nput t ed dat a f or t he act i ve pr oper t y sel ect i ons.
The Enabl e Tabul ar Pr oper t i es check box mak es t he ot her
pages act i ve f or speci f i cat i on. Deact i vat i ng t hi s check box
pur ges t he t ab of any t abul ar pr oper t y dat a i t mi ght have
pr evi ousl y cont ai ned.
Act ivat ing t he Enable
Tabular Propert ies
checkbox will make t he
Opt ions t ree, I nformat ion
t ree, and Not es page
available.
2- 71
Basis for Tabular Ent halpies
This group becomes act ive aft er t he Enable Tabular Propert ies checkbox
is clicked. I t allows you t o select bet ween t he ent halpy basis for t abular
calculat ions:
H = 0 K, ideal vapour ( Legacy HYSI M basis)
H = Heat of for mat ion at 25 C, ideal vapour
Opt ions Tree Configurat ion
You can t arget a propert y t hrough t he t hree pages available in t he
Opt ions t ree. To expand t he t r ee, click t he + in front of t he Opt ions
label in t he Tabular Package group. This allows t he All Propert ies,
Physical, and Thermodynamics pages t o be visible. Each one of t hese
pages consist s of a five column mat rix t able.
Propert y Type
The All Proper t ies page consist s of sevent een proper t ies which include
bot h t he Physical and Thermodynamic pr opert ies. These pr opert ies
have t hen been subdivided int o t wo groups and displayed again on
eit her t he Physical or Thermodynamics page. These propert ies ar e
list ed in t he t able below, along wit h t he subgroup t hat t hey belong t o:
K- value ( V/ L1) [ Thermodynamic]
K- value ( V/ L2) [ Thermodynamic]
K- value ( L1/ L2) [ Thermodynamic]
Ent halpy( L) [ Thermodynamic]
Ent halpy( V) [ Thermodynamic]
Lat ent Heat [ Thermodynamic]
Fi gur e 2. 50
2- 72
Heat Capacit y( L) [ Thermodynamic]
Heat Capacit y( V) [ Thermodynamic]
Heat of Mixing[ Thermodynamic]
Viscosit y ( L) [ Physical]
Viscosit y ( V) [ Physical]
Thermal Cond ( L) ) [ Physical]
Thermal Cond ( V) ) [ Physical]
Surface Tension[ Physical]
Densit y ( L) [ Physical]
Ent ropy( L) [ Thermodynamic]
Ent ropy( V) [ Thermodynamic]
Use UniSim Design/ Use PPDS/ Use CCO
The checkboxes in t he Use UniSim Design, Use PPDS and Use CCO
columns allow you t o respect ively select among t he Honeywell, PPDS
and ot her component dat abases such as DI PPR. Depending on t he
propert y t ype select ed, t he PPDS library or Component Curve Opt ion
may not be available. When t he PPDS library or Component Curve
Opt ion is available, t he checkbox changes from light grey t o whit e.
Composit ion Basis
The Composit ion Basis allows you t o select t he Basis ( mole, mass, or liq
volume) on which t he mixing rule is applied. When you select a
propert y t ype t he Composit ion Basis becomes act ive for t hat propert y.
The available opt ions can be accessed from t he drop- down list wit hin
t he cell of each propert y select ed.
The default mixing rule which is applied when calculat ing t he overall
propert y is shown in t he following form:
Mixing Paramet er
The last column in t he mat rix t able is t he Mixing Paramet er. This allows
you t o specify t he coefficient ( f ) t o use for t he mixing rule calculat ions.
Not ice t hat t he default value is 1. 00. The value t hat UniSim Design uses
as t he default is dependent on t he propert y select ed. For inst ance, if
you select Liquid Viscosit y as t he propert y t ype, UniSim Design uses
0. 33 as t he default for t he Mixing Paramet er.
(2.47)
The PPDS dat abase and
Component curve Opt ion
are opt ional t abular
feat ure. Cont act your
Honeywell for furt her
informat ion.
Property
mix
x
i
Property
i
f
i
1
f
--
=
2- 73
I f you are using t he PPDS dat abase, you can modify t he mixing rule
paramet ers for any propert y wit h t he except ion of t he vapour viscosit y
and vapour t hermal conduct ivit y. The paramet ers for t hese propert ies
are set int ernally t o t he appropriat e PPDS mixing rule.
I nformat ion Tree Configurat ion
Aft er propert ies are act ivat ed on one of t he t hree pages in t he Opt ions
t ree, t he propert y appears in t he I nformat ion t ree. This t ree may be
expanded by clicking t he + in front of t he I nformat ion label in t he
Tabular Package gr oup.
A component may be t arget ed by clicking in any cell in t he component s
column. For example, if Propane was t he component of int erest , click in
any cell in t he t hird column. Once t he component is t arget ed, select t he
Cmp Pr op Det ail but t on t o access t he PropCurve view. Most of t he
informat ion cont ained in t he PropCurve view is displayed on t he
I nformat ion pages and can also be changed t here.
Cmp Plot s But t on
The Cmp Plot but t on accesses t he plot of Temperat ure vs. t he select ed
Propert y Type. The Variables group shows t he propert y used for t he X
Fi gur e 2. 51
I t is import ant t o not e
t hat t he Heat of Mixing
propert y does not creat e
a page in t he I nformat ion
t ree. I nst ead it will creat e
a unique t ree in t he
Tabular Package group.
See Suppl y i ng Tabul ar
Dat a for furt her
PropCurve view.
2- 74
and Y axis ( Ent halpy in t his case) .
UniSim Design can only plot four curves at a t ime. The Curve Select ion
group list s t he component s which are plot t ed on t he graph. The default
is t o plot t he first four component s in t he component list . You can
replace t he default component s in t he Curve Select ion group wit h ot her
component s by using t he drop- down list in each cell.
Select t he component you want t o add t o t he Curve Select ion group.
The new component replaces t he previously select ed component in t he
Curve Select ion group, and UniSim Design redraws t he graph,
displaying t he dat a of t he new component .
UniSim Design uses t he current expressions t o plot t he graphs, eit her
from t he UniSim Design library or your supplied regressed dat a.
Fi gur e 2. 52
Obj ect inspect t he plot
area t o access t he Graph
Cont rol view. Refer t o
Sect i on 10. 4 - Gr aph
Cont r ol of t he Uni Si m
Desi gn User Gui de for
more informat ion.
2- 75
Heat of Mixing Tree
When t he Heat of Mixing propert y is act ivat ed on eit her t he All
Propert ies or t he Thermodynamic page in t he Opt ions t ree, a new t r ee
get s added t o t he root of t he t r ee in t he Tabular Propert ies group. This
t ree may be expanded by pressing t he + in front of t he Heat of Mixing
label in t he t ree. The pages in t he t ree correspond t o t he component s in
t he fluid package.
Heat of Mixing Page
This page is only visible when Heat of Mixing is select ed on t he All
Propert ies or Thermodynamic pages. I t consist s of t he following
obj ect s:
Fi gur e 2. 53
UNI FAC VLE UniSim Design uses t he UNI FAC VLE est imat ion met hod t o
calculat e t he binary coefficient s. This overwrit es any
exist ing coefficient s.
UNI FAC LLE Same as UNI FAC VLE, except t he LLE est imat ion met hods
are used.
Temper at ur e The reference t emperat ure at which t he UNI FAC
paramet ers are calculat ed.
2- 76
Composit ion Pages
The Composit ion pages in t he Heat of Mixing t ree are very similar t o t he
pages cont ained in t he I nformat ion t ree. Click t he View Det ails but t on
t o access a modified PropCurve view.
The only difference is t hat t here is no Coeff t ab. Most of t he informat ion
cont ained in t he PropCurve view is displayed on t he I nformat ion pages,
where it can be modified.
Not es Page
Any comment s regarding t he t abular dat a or t he simulat ion in general
may be displayed here.
Supplying Tabular Dat a
When you have specified t he flowsheet propert ies for which you want t o
use t he Tabular Package, you can change t he dat a UniSim Design uses
in calculat ing t he propert ies. UniSim Design cont ains a dat a file wit h
regressed coefficient s and t he associat ed equat ion shape, for most
component s.
To illust rat e t he met hod of supplying dat a, use Met hane as a component
and Liquid Ent halpy as t he Propert y. From t he Ent halpy ( L) Tabular
Package gr oup, select t he Met hane cell as t he component and click t he
Cmp. Prop. Det ail but t on. The Variables t ab of t he PropCurve view is
Fi gur e 2. 54
See Suppl y i ng Tabul ar
Dat a for furt her
PropCurve view.
I f Heat of Mixing is used,
you can access t he Prop
Curve by select ing t he
component and t hen click
t he View Det ails but t on.
Alt hough it should be
not ed t hat t his view does
not include t he Coeffs t ab.
2- 77
displayed as shown below:
The PropCurve propert y view cont ains t he following t abs:
Variables Tab
The Variables t ab is t he first t ab of t he PropCurve propert y view. I t
cont ains four groups, X- Variable, Y- Var iable, Q- Variable, and Equat ion
Form. The Variables t ab is shown in t he previous figure.
X-Variable Group
This group cont ains informat ion relat ing t o t he X- Variable and is
described below.
Fi gur e 2. 55
Tab Descr i pt i on
Var i abl es Specify t he equat ion shapes and power funct ions for t he
propert y.
Coef f Displays t he current coefficient s for t he select ed equat ion.
Tabl e Current t abular dat a for t he propert y ( library or user
supplied) .
Pl ot s Plot s of t he propert y using t he t abular dat a and t he
regressed equat ion.
Not es User supplied descript ive not es for t he regression.
Cel l s Descr i pt i on
X Since all propert ies are measured versus Temperat ure, t his
cell always shows Temperat ure when using t he Tabular
Package.
Uni t Displays t he unit s for t he t emperat ure values. You cannot
change t he unit s here. The UniSim Design int ernal unit s for
Temperat ure, K, are always used.
2- 78
Y-Variable Group
This group cont ains all infor mat ion relat ing t o t he Y- Variable.
Q-Variable Group
This group cont ains all informat ion relat ing t o t he Q Variable. This
Shape This is t he shape of t he X variable. The choices for t he X
Shape can be accessed using t he drop- down list in t he cell.
There are 29 available shapes. Use t he scroll bar t o move
t hrough t he list . I n t his case, t he shape select ed is Xv ar : x .
This means t hat t he X variables in t he equat ion are equal t o
X, which represent s t emperat ure. I f LogX: log10( x) is
select ed as t he X Shape, t hen t he X variables in t he
equat ion are replaced by log10( x) .
Shape Nor m This is a numerical value used in some of t he X Shapes. I n
t he drop- down list for X Shape, not ice t hat t he second
choice is Xreduced: x/ norm. The x/ norm t erm, where norm
= 190. 70, replaces t he X variable in t he equat ion. You can
change t he numerical value for Norm in t he cell.
Ex ponent Allows you t o apply a power t erm t o t he X t erm, for
example, X
0. 5
.
Eqn
Mi ni mum
Defines t he minimum boundary for t he X variable. When a
flowsheet calculat ion for t he propert y is out side t he range,
UniSim Design uses an int ernal met hod for ext rapolat ion of
t he curve. This met hod is dependent on t he Propert y being
used. See t he Equat ion Form sect ion.
Eqn
Max i mum
Defines t he maximum boundary for t he X variable. When a
flowsheet calculat ion for t he propert y is out side t he range,
UniSim Design uses an int ernal met hod for ext rapolat ion of
t he curve. This met hod is dependent on t he Propert y being
used. See t he Equat ion Form sect ion.
Y This is t he propert y chosen for Tabular calculat ions.
Uni t Displays t he unit s for t he Y variable. You cannot change t he
unit s here, it must be done t hrough t he Basis Manager
( Preferences opt ion) .
Shape This is t he shape of t he Y variable. The choices for t he Y Shape
are available using t he drop- down list wit hin t he cell. There
are 32 shapes select ed. Use t he scroll bar t o move t hrough t he
list . I n t his case, t he shape chosen is Yvar: y. This means t hat
t he Y variables in t he equat ion are equal t o Y, which represent s
ent halpy. I f LogY: log10( y) is chosen as t he Y Shape, t hen t he
Y variables in t he equat ion are replaced by log10( y) .
Shape
Nor m
This is a numerical value used in some of t he Y Shapes. I n t he
drop- down list for Y Shape, not ice t hat t he second choice is
Yreduced: y/ norm. The Y variable in t he equat ion is replaced
by t he y/ norm value. This numerical value can be changed
wit hin t he cell.
Ex ponent Allows you t o apply a power t erm t o t he Y t erm, for example,
Y
0. 5
.
2- 79
Variable is used in some of t he X and Y Variable equat ions.
Coefficient s Group
This group is only visible in t he Heat of Mixing page when it is an act ive
propert y.
The Coefficient s gr oup cont ains t he coefficient values eit her obt ained
from t he UniSim Design dat abase, or regressed from dat a supplied in
t he Table t ab.
Equat ion Form
Depending on which propert y you have select ed, UniSim Design select s
a default Equat ion Shape. You have t he opt ion of using t his equat ion or
an alt ernat ive one. You can select a different equat ion from t he dr op-
down list associat ed wit h t his cell. This list cont ains 33 available
equat ions t o choose from.
Cel l Descr i pt i on
Q Represent s t he Q variable which is always Pressure.
Uni t Displays t he unit s for t he Q Variable, which are always t he
default int ernal unit s of pressure, kPa.
Def aul t This is t he default numerical value given t o t he Q Variable
which can be modified wit hin t he cell.
Fi gur e 2. 56
Fi gur e 2. 57
2- 80
When UniSim Design cannot regress t he dat a t o produce equat ion
coefficient s for t he select ed equat ion shape, t he message Non-
Regressable appears on t he right of t he drop- down list . You can st ill use
t he equat ion shape, but you have t o manually input t he coefficient s.
Coeff Tab
This t ab displays t he current coefficient s for t he specified equat ion.
Not ice t hat t his view also cont ains t he Equat ion Form group, allowing
you t o change t he equat ion from t his t ab.
The Coefficient s gr oup cont ains t he coefficient values eit her obt ained
from t he UniSim Design dat abase, or regressed from dat a supplied in
t he Table t ab.
The checkboxes supplied next t o each coefficient value allow you t o
inst ruct UniSim Design not t o regress cert ain coefficient s, t hey will
remain at t he fixed value ( default or user supplied) during regression.
Fi gur e 2. 58
Fi gur e 2. 59
Some equat ion shapes
only allow you t o supply
coefficient s direct ly. You
are informed if t he
equat ion shape cannot
have t abular dat a
regressed t o it .
The X, Y, and Q
variables and t heir unit s
are displayed for
reference only. They
can not be modified.
2- 81
Table Tab
You can supply your t abular dat a before or aft er select ing t he Equat ion
Shape. To ent er dat a, select t he Table t ab.
I f t he component is from t he UniSim Design library, 20 point s are
generat ed bet ween t he current Min and Max t emperat ur es. I f you need
t o supply dat a, click t he Clear Dat a but t on. You can also add your dat a
t o t he UniSim Design default dat a and have it included in t he
regression.
Supplying Dat a
I f you are going t o supply dat a, select t he unit cell under t he X and Y
variable columns and press any key t o open t he drop- down list . From
t he list you can change t o t he appropriat e unit s for your dat a.
The procedure for supplying dat a is as follows:
1. Select t he appropriat e unit s for your dat a.
2. Clear t he exist ing dat a wit h t he Cl ear Dat a but t on, or move t o t he
locat ion t hat you want t o overwrit e.
3. Supply your dat a.
4. Supply Net Weight Fact ors if desired.
Q- Column
This column cont ains t he Pressure variable. The presence of t his ext ra
variable helps in providing bet t er regression for t he dat a. As wit h t he X
and Y variables, t he unit s for pressure can be changed t o any of t he
unit s available in t he drop- down list .
Fi gur e 2. 60
To delet e a part icular
dat a point , highlight t he
dat a point and press t he
DELETE key.
Coefficient s calculat ed
using t he delet ed dat a
are st ill present on t he
Coeff t ab unt il t he
Regress but t on is
clicked.
2- 82
Wt Fact or
You can apply weight ing t o individual dat a point s. When t he regression
is performed, t he point s wit h higher weight ing fact ors are t reat ed
preferent ially, ensuring t he best fit t hrough t hat region.
Regressing t he Dat a
Aft er you have pr ovided t he dat a, you need t o updat e t he equat ion
coefficient s. Click t he Regress but t on t o have UniSim Design regress
your dat a, generat ing t he coefficient s based on t he current shapes. I f
you t hen change any of t he equat ion shapes, t he dat a you supplied is
regressed again. You can re- ent er t he regression package and select a
new shape t o have your dat a regressed.
Dat a Ret ent ion
Whenever experiment al dat a is supplied, it is ret ained by UniSim
Design in memory and is st ored in t he case. At a lat er dat e, you can
come back int o t he Tabular Package and modify dat a for t he Propert y,
and UniSim Design regr esses t he dat a once again.
Plot Tab
To examine how t he current equat ions and coefficient s represent t he
propert y, select t he Plot s t ab t o view t he plot .
Only t he select ed component ( in t his case Met hane) is displayed. The
plot cont ains t wo curves, one plot t ed wit h t he regressed equat ion and
t he ot her wit h t he Table values. I f t he Tabular values supplied on t he
Fi gur e 2. 61
Use t he Plot but t on on
t he Tabular t ab t o
display up t o four
component curves on
t he same graph.
2- 83
Table t ab are in different unit s, t hey are st ill plot t ed here using t he
UniSim Design int ernal unit s. This provides a means for gauging t he
accuracy of t he regression. I n t his example, t he t wo curves overlap
each ot her, such t hat it appears t o only show one curve.
Besides displaying t he component curve, t his view also displays t he
number of point s used in det ermining t he t abular equat ion ( in t his case
20) . As well, t he x- Axis group displays t he Min ( 91. 7) and Max ( 169) x-
values on t he curve.
You can change t he Min and Max x- axis values and have UniSim Design
ext end t he curve appr opriat ely. Place t he cur sor in t he Min cell and t ype
in a new value. For example, t ype 70. This replaces 91. 7, and UniSim
Design ext ends t he curve t o include t his value. Similarly, you can
change t he Max value, and have UniSim Design ext end t he curve t o
include t his new value. Type 180 t o replace t he Max value of 169. 00.
The new curve is shown below.
Not es Page
The Not es page is used for supplying a descript ion t o associat e wit h t he
Tabular Dat a j ust ent ered.
When you have finished providing all necessary dat a, close t he
PropCurve view and ret urn t o t he Tabular t ab of t he Fluid Package
propert y view. You can now cont inue t o supply dat a for t he ot her
component s, if you want . The propert ies t hat you have specified t o be
calculat ed wit h t he Tabular package car ry t hrough int o t he Flowsheet .
2. 4. 8 Not es Tab
The Not es t ab allows you t o provide document at ion t hat is st ored wit h
t he Fluid Package. When you export a Fluid Package, any Not es
associat ed wit h it are also export ed. When you want t o import a Fluid
Fi gur e 2. 62
To review all not es wit hin
t he fluid package, refer t o
Sect i on 7.20 - Not es
Manager of t he Uni Si m
2- 84 Uni Si m Ther mo Pr oper t y Vi ew
2- 84
Package at a lat er dat e, t he Not es t ab allows you t o view informat ion
about t he Fluid Package.
2. 5 UniSim Thermo Propert y
View
The Fluid Package UniSim Thermo propert y view can be accessed by
select ing t he UniSim Thermo checkbox in t he Advanced
Thermodynamics group. UniSim Thermo consist s of eight t abs and is
based on t he UniSim Thermo t hermodynamics framework. These t abs
include informat ion pert aining t o t he part icular fluid package select ed
for t he case. When you creat e a new fluid package and select t he
UniSim Thermo radio but t on t he Set Up view appears as shown below.
Fi gur e 2. 63
Removes t he Fluid Package
from t he case. You must
confirm t hat you want t o
delet e t he Fluid Package.
You can input a name
for t he Fluid Package
in t his cell.
The propert y packages
select ed for t he vapor and
liquid phases are shown in
t his st at us bar.
Select t he but t on t o
edit propert ies at t he
fluid package level.
2- 85
2. 5. 1 Set Up Tab
The Set Up t ab cont ains t he Model Select ion, Model Phase, Model
Opt ions, Ext ended Set up, Advanced Thermodynamics, and Component
List Select ion groups for t he Fluid Package pr opert y view in UniSim
Thermo.
Aft er a Model is select ed, Propert ies and Met hod opt ions are displayed
in t he Model Opt ions gr oup. The propert ies and met hods t hat are
displayed are dependent on t he select ed Model.
The following sect ions provide an overview of t he various models, as
well as det ails on t he various groups t hat appear on t he Set Up t ab.
Model Select ion
I n t he Model Select ion group, you have access t o t he list of default
propert y models t hat are available in UniSim Design- UniSim Thermo.
The availabilit y of t he models depends on t he Vapour or Liquid Model
Phase select ed for your syst em. Using t he radio but t ons, t he models
are filt ered for vapor and liquid models. A model for t he vapor and
Fi gur e 2. 64
I nformat ion on Propert y and
calculat ion Met hods depending on
t he Model select ed. Use t he drop-
down list t o select alt ernat ive
calculat ion met hods.
Select t he
Vapor or Liquid
Model Phase
using t he radio
but t ons.
Select a Component List here. I t is not recommended
t o use t he Mast er Component List .
Addit ional
I nformat ion on
t he Model
select ed.
Select a flash calculat ion
met hod here. The but t ons
below are used t o set up t he
ext ended cust om propert y
package and ext ended flash.
Select a propert y
model for t he
vapor and liquid
phase.
To creat e or add propert y
packages and propert ies,
refer t o t he UniSim
Thermo online help in t he
development kit .
2- 86
liquid phase is required and displayed in t he Propert y Pkg st at us bar.
* Described in the following sections.
For det ailed informat ion on UniSim Thermo Models t hat are available in
UniSim Design, refer t o t he Honey w el l Uni Si m Ther mo Ref er ence
Gui de.
Equat ions of St at e
Equat ions of st at e are used t o model t he behaviour of single, t wo, and
t hree phase syst ems. For oil, gas and pet rochemical applicat ions, t he
Peng Robinson Equat ion of St at e is generally t he recommended
propert y model. I t rigorously solves most single phase, t wo phase and
t hree- phase syst ems wit h a high degree of efficiency and reliabilit y.
The enhancement s t o t his equat ion of st at e ( UniSim DesignPR) , enable
it t o be accurat e for a variet y of syst ems over a wide range of
condit ions. The equat ion of st at e met hods and t heir specific
applicat ions are described below:
Vapor Phase The Vapor Phase cont ains a list of Equat ions of St at e*
used t o model t he vapor phase in t he Model Select ion
Group.
Li qui d Phase The Liquid Phase cont ains a list of t he various Equat ions
of St at e* , Act ivit y Models* , and semi- empirical met hods
( Chao Seader & Grayson St reed) t o charact erize t he
liquid phase of a chemical syst em.
EOS Descr i pt i on
Av ai l abl e
f or
I deal Gas PV= nRT can be used t o model t he Vapor
Phase but is only suggest ed for ideal
syst ems under moderat e condit ions.
Vapor
Phase only
PR
Peng-
Robi nson
This model is ideal for VLE calculat ions as
well as calculat ing liquid densit ies for
hydrocarbon syst ems. However, in sit uat ions
where highly non- ideal syst ems are
encount ered, t he use of Act ivit y models is
recommended.
Vapor and
Liquid
Phase
PR- eTher mo The PR- eThermo EOS is similar t o t he PR
EOS wit h several enhancement s t o t he
original PR equat ion. I t ext ends t he range of
applicabilit y and bet t er represent s t he VLE of
complex syst ems.
Vapor and
Liquid
Phase
PRSV
Peng-
Robi nson
St r y j ek - Ver a
This is a t wo- fold modificat ion of t he PR
equat ion of st at e t hat ext ends t he
applicat ion of t he original PR met hod for
moderat ely non- ideal syst ems. I t provides a
bet t er pure component vapor pressure
predict ion as well as a more flexible mixing
rule t han Peng robinson.
Vapor and
Liquid
Phase
Refer t o t he Honeyw el l
Uni Si m Ther mo
more det ailed informat ion
on t he available Equat ions
of St at e.
2- 87
Act ivit y Models
Alt hough Equat ion of St at e models have proven t o be reliable in
predict ing t he propert ies of most hydrocarbon based fluids over a wide
non- polar or slight ly polar component s. Non- ideal syst ems at low t o
moderat e pressure are best modeled using Act ivit y Models. Act ivit y
models only perform calculat ions for t he liquid phase. This requires you
t o specify a calculat ion met hod for t he modeling of t he vapor phase.
SRK
Soav e-
Redl i ch-
Kw ong
I n many cases it provides comparable result s
t o PR, but it s range of applicat ion is
significant ly more limit ed. This met hod is not
as reliable for non- ideal syst ems.
Vapor and
Liquid
Phase
Br aun K10 This model is st rict ly applicable t o heavy
hydrocarbon syst ems at low pressures. The
model employs t he Braun convergence
pressure met hod, where, given t he normal
boiling point of a component , t he K-value is
calculat ed at syst em t emperat ure and 10
psia ( 68.95 kPa) .
Vapor and
Liquid
Phase
KD
Kabadi
Danner
This model is a modificat ion of t he original
SRK equat ion of st at e, enhanced t o improve
t he vapor- liquid- liquid equilibrium
calculat ions for wat er- hydrocarbon syst ems,
part icularly in dilut e regions.
Vapor and
Liquid
Phase
Lee- Kesl er -
Pl ock er
This model is t he most accurat e general
met hod for non- polar subst ances and
mixt ures.
Vapor and
Liquid
Phase
Redl i ch-
Kw ong
The Redlich- Kwong equat ion generally
provides result s similar t o Peng- Robinson.
Several enhancement s are made t o t he PR
as described above which make it t he
preferred equat ion of st at e.
Vapor
Phase only
Sour Peng-
Robi nson
Combines t he PR equat ion of st at e and
Wilson' s API - Sour Model for handling sour
wat er syst ems.
Vapor and
Liquid
Phase
Vi r i al This model enables you t o bet t er model
vapor phase fugacit ies of syst ems displaying
st rong vapor phase int eract ions. Typically
t his occurs in syst ems cont aining carboxylic
acids, or compounds t hat have t he t endency
t o form st able hydrogen bonds in t he vapor
phase. I n t hese cases, t he fugacit y
coefficient shows large deviat ions from
idealit y, even at low or moderat e pressures.
Vapor only
Zudk ev i t ch-
Jof f ee
This is a modificat ion of t he Redlich Kwong
equat ion of st at e, which reproduces t he pure
component vapor pressures as predict ed by
t he Ant oine vapor pressure equat ion. This
model is enhanced for bet t er predict ion of
vapor- liquid equilibrium for hydrocarbon
syst ems, and syst ems cont aining Hydrogen.
Vapor and
Liquid
Phase
EOS Descr i pt i on
Av ai l abl e
f or
2- 88
The following Act ivit y Models are available for modelling t he liquid
phase of a syst em:
I deal Sol ut i on Assumes t he volume change due t o mixing is zero. This
model is more commonly used for solut ions comprised
of molecules not t oo different in size and of t he same
chemical nat ure.
Regul ar
Sol ut i on
This model eliminat es t he excess ent ropy when a
solut ion is mixed at const ant t emperat ure and volume.
The model is recommended for non- polar component s in
which t he molecules do not differ great ly in size. By t he
at t ract ion of int ermolecular forces, t he excess Gibbs
energy may be det ermined.
represent ing VLE, LLE, and VLLE phase behaviour.
Gener al NRTL This variat ion of t he NRTL model uses five paramet ers
and is more flexible t hen t he NRTL model. The following
equat ion format is used for t he equat ion paramet ers: t
and o:
Apply t his model t o syst ems:
component s.
where you require simult aneous solut ion of VLE
and LLE, and t here exist s a wide boiling point or
UNI QUAC Uses st at ist ical mechanics and t he quasi- chemical
t heory of Guggenheim t o represent t he liquid st ruct ure.
The equat ion is capable of represent ing LLE, VLE, and
VLLE wit h accuracy comparable t o t he NRTL equat ion,
but wit hout t he need for a non- randomness fact or.
Wi l son First act ivit y coefficient equat ion t o use t he local
composit ion model t o derive t he Gibbs Excess energy
expression. I t offers a t hermodynamically consist ent
approach t o predict ing mult i- component behaviour from
regressed binary equilibrium dat a. However t he Wilson
model cannot be used for syst ems wit h t wo liquid
phases.
Chi en- Nul l Provides consist ent framework for applying exist ing
Act ivit y Models on a binary by binary basis. I t allows you
t o select t he best Act ivit y Model for each pair in your
case.
Mar gul es This was t he first Gibbs excess energy represent at ion
developed. The equat ion does not have any t heoret ical
basis, but is useful for quick est imat es and dat a
int erpolat ion.
represent ing VLE, LLE and VLLE phase behaviour.
Refer t o t he Honey w el l
Uni Si m Ther mo
more det ailed
available Act ivit y models.
t
ij
A
ij
B
ij
T
-----
C
ij
T
2
----- F
ij
T G
ij
T ln + + + + =
o
ij
o1
ij
o2
ij
T + =
2- 89
Vapor Pressure Models
Vapor pressure K- value models may be used for ideal mixt ures at low
pressures. I deal mixt ures include hydr ocarbon syst ems and mixt ures
such as ket ones and alcohols, where t he liquid phase behaviour is
approximat ely ideal. The Vapour Pressure models may also be used as
a first approximat ion for non- ideal syst ems.
Chao Seader & Grayson St reed Models
The Chao Seader and Grayson St reed met hods are older, semi-
empirical met hods. The Grayson St reed correlat ion is an ext ension of
t he Chao Seader met hod wit h special emphasis on hydrogen. Only t he
equilibrium dat a produced by t hese correlat ions is used by UniSim
Design. The Lee- Kesler met hod is used for liquid and vapor ent halpies
and ent ropies.
Van Laar This equat ion fit s many syst ems quit e well, part icularly
for LLE component dist ribut ions. I t can be used for
syst ems t hat exhibit posit ive or negat ive deviat ions from
Raoult s Law; however, it cannot predict maxima or
minima in t he act ivit y coefficient . Therefore it generally
performs poorly for syst ems wit h halogenat ed
hydrocarbons and alcohols.
UNI FAC VLE/
LLE
Bot h UNI FAC VLE and UNI FAC LLE use t he solut ion of
at omic groups model in which exist ing phase equilibrium
dat a for individual at omic groups is used t o predict t he
phase equilibria of syst em of groups for which t here is
no dat a. The group dat a is st ored in specially developed
int eract ion paramet er mat rices for bot h VLE and LLE
propert y packages.
Ant oi ne This model is applicable for low pressure syst ems t hat
behave ideally.
Br aun K10 This model is st rict ly applicable t o heavy hydrocarbon
syst ems at low pressures. The model employs t he Braun
convergence pressure met hod, where, given t he normal
boiling point of a component , t he K- value is calculat ed at
syst em t emperat ure and 10 psia ( 68.95 kPa) .
Esso Tabul ar This model is st rict ly applicable t o hydrocarbon syst ems
at low pressures. The model employs a modificat ion of
t he Maxwell- Bonnel vapor pressure model.
2- 90
Ext ended Propert y Package & Ext ended Flash
The Ext ended Propert y Package model allows t he user t o incorporat e
exist ing ext ernal propert y packages wit h minimum modificat ions t o
t hem. You may set up a number of different propert y packages using
ext ended met hods, which perform different t hermodynamic
calculat ions, handle different dat abases for pure compound propert ies
and/ or int eract ion paramet ers.
Unlike default UniSim Thermo met hods, which are st at eless, Ext ended
Propert y Packages can keep and carry st at e informat ion. St at e
informat ion refers t o dat a such as pure compound and mixt ure
informat ion. I n t he implement at ion of an Ext ended Propert y Package,
t he calls bet ween different propert y calculat ion rout ines can be made
direct ly wit hout a need t o use COM int erfaces. You can mix and mat ch
Ext ended Propert y met hods wit h UniSim Thermo default propert y
calculat ion met hods. This can be set up in t he XML model file.
To set up an Ext ended Propert y Package t wo XML model files are
required, one for vapor phase and one for liquid phase. Bot h XML model
files must cont ain t he same package name. When select ing an
ext ended package for calculat ions, t he same ext ended package must
be select ed for bot h vapor and liquid phase.
The Ext ended PropPkg Set up but t on is accessed by select ing t he
appropriat e ext ended package for bot h t he vapor and liquid model
phases. The Ext ended PropPkg view is shown below for an example
Chao Seader Use t his met hod for heavy hydrocarbons, where t he
pressure is less t han 10342 kPa ( 1500 psia) , and
t emperat ures range bet ween - 17.78 and 260 C ( 0- 500
F) .
Gr ay son St r eed Recommended for simulat ing heavy hydrocarbon
syst ems wit h a high hydrogen cont ent .
The Uni Si m Ther mo onl i ne hel p i s l ocat ed i n t he Uni Si m
Ther mo DK ( devel opment k i t ) . You need t o set up t he Uni Si m
Ther mo DK f r om t he i nst al l at i on di sk .
Refer t o Ext ended
Propert y Packages and
Flash sect ion in t he
Honey w el l Uni Si m
Ther mo Pr ogr ammer s
Gui de for det ailed
informat ion on how t o add
ext ended flash and
ext ended propert y
packages.
To set up an Ext ended
Propert y Package for
calculat ions, you must
select t he same ext ended
package for bot h t he
vapor and liquid phases.
2- 91
package wit h Ext Pkg as t he name of t he XML model file.
The Ext ended Propert y Package Set up includes a descript ion of t he
package and t he set up files. The Add but t on allows you t o browse
Set up files for t he Ext ended Propert y package. The On View but t on
allows you t o see and configure t he associat ed views of your select ed
ext ended met hod.
The Ext ended Flash model provides t he user wit h t he capabilit y t o use
cust om flash calculat ion met hods. UniSim Thermo also allows t he user
t o mix and mat ch different flash met hods. For example, t he user can
implement a PV ( pressure- vapor fract ion) flash in an Ext ended Flash
package and use t he exist ing UniSim Thermo PT flash ( pressure-
t emperat ure) . The flash opt ion can be set up t hrough t he Flash Family,
which is locat ed in t he Model and Flash XML sect ion of t he UniSim
Thermo online help.
A Ext ended Flash also requir es a flash XML model file t o set up t he flash
family name. The Ext ended Flash Set up but t on is accessed by select ing
t he appropriat e XML model filename. The Ext ended Flash Set up view is
shown below for an example flash wit h Ext endedFlash as t he name of
Fi gur e 2. 65
FI F
2- 92
t he XML model file.
Ext ended Propert y Package and Ext ended Flash can be used t oget her or
separat ely.
Advanced Thermodynamics
The Advanced Thermodynamics group allows you t o model t he fluid
package based on t he UniSim Thermo framework.
The Advanced Thermodynamics group cont ains t he following but t ons:
I mpor t . Allows you t o import an exist ing UniSim Thermo
propert y package.
Ex por t . Allows you t o export a UniSim Thermo based propert y
package.
Regr essi on. Allows you t o export t he fluid package direct ly int o
UniSim Thermo Workbench where t he fluid package can be
manipulat ed by a broad select ion of est imat ion met hods and
Fi gur e 2. 66
Fi gur e 2. 67
The i mpor t ed/ ex por t ed Uni Si m Ther mo Pr oper t y pack age
can be used i n Uni Si m Desi gn, DI STI L, and Uni Si m Ther mo
Wor k bench.
Refer t o t he
Ther mody nami cs
Wor k bench Guide of t he
Concept ual Process
Design Suit e for more
informat ion on UniSim
Thermo Workbench.
2- 93
dat a regr ession. Once t he regression is complet e in t he UniSim
Thermo Workbench, t he regressed fluid package can be
import ed back t o UniSim Design.
When you click t he Regression but t on t he following view appears:
Component List Select ion
You must select a Component List t o associat e wit h t he current Fluid
Package from t he Component List Select ion drop- down list . Component
List s are st ored out side of t he Fluid Package Manager in t he
Component s Manager and may cont ain library, hypot het ical, and
elect rolyt e component s. To view t he Component List View, click on t he
You must have t he Concept ual Pr ocess Desi gn Sui t e i nst al l ed
w i t h Uni Si m Ther mo Wor k bench l i censi ng i n or der t o appl y
t he Regr essi on f eat ur e i n Uni Si m Desi gn.
Fi gur e 2. 68
Regr essi on Descr i pt i on
St ar t Regr essi on This but t on is similar t o export ing a fluid package. I t
allows you t o select a file t o be opened up in UniSim
Thermo Workbench for regression analysis.
Load Regr essi on This but t on is similar t o import ing a fluid package. A
menu of exist ing packages appear, allowing you t o
ret rieve informat ion from a previously regressed
package.
Wr i t i ng Fl ui d
Pack age
A st at us indicat or t o indicat e t hat a new fluid package
is being generat ed.
St ar t i ng Uni Si m
Ther mo
Wor k bench
A st at us indicat or t o indicat e t hat UniSim Thermo
Workbench is st art ing aft er t he fluid package is
generat ed.
The r egr essed f l ui d pack age i s saved w i t h * .ct f ex t ensi on
al ong w i t h t w o def aul t t ag f i l es, cc.XML, and pm.XML. You
must have al l t hr ee f i l es sav ed i n t he same di r ect or y t o
access t he r egr essed f l ui d pack age.
2- 94
View but t on.
Model Opt ions
When you have select ed a Model, addit ional propert y and opt ion
met hods are displayed on t he right side of t he Set Up t ab in t he Model
Opt ions group. This informat ion is direct ly relat ed t o t he Model and
phase select ed.
The Model opt ions group shows each propert y and what calculat ion
met hod is used for t hat propert y.
For example, t he Peng- Robinson Model Opt ions for t he vapor phase are
shown below:
The Ent halpy propert y uses t he Peng- Robinson Ent halpy calculat ion
met hod. The met hod opt ions which are displayed in red have
alt ernat ive calculat ion met hods. By placing your cursor on t he drop-
down list , you have a choice t o select t he Lee- Kesler calculat ion met hod
I t i s not r ecommended f or user s t o at t ach t he Mast er
Component Li st t o any Fl ui d Pack age. I f onl y t he mast er l i st
ex i st s, by def aul t a cl oned v er si on of t he Mast er Component
Li st i s cr eat ed ( cal l ed Component Li st - 1) . Thi s l i st i s
sel ect ed i ni t i al l y w hen a new Fl ui d Pack age i s cr eat ed.
A model must be sel ect ed f or bot h t he vapor and l i qui d
phases.
Fi gur e 2. 69
2- 95
for Ent halpy.
The Ent ropy and Cp propert ies may also be alt ered t o use t he Lee-
Kesler calculat ion met hods for t he Peng- Robinson EOS. I f t he propert y
met hod is alt ered, it appears in blue. The informat ion in black are
default met hods for UniSim Design- UniSim Thermo. Met hods ar e added
in t he XML file and t hen can be seen in t he met hod gr oup for t he
propert y select ed. Refer t o t he Wizards & Add- I ns sect ion of t he UniSim
Thermo online help locat ed in t he UniSim Thermo Development Kit t o
help in adding new propert ies, propert y packages, and flash.
EOS Ent halpy, Ent ropy & Cp Met hod Specificat ion
Wit h most of t he Equat ions of St at es, you may have t wo or t hree
alt ernat ive calculat ion met hods for ent halpy, ent ropy, and Cp. The
propert y calculat ion met hods t hat are available include: t he EOS
select ed, and t he Lee- Kesler met hod.
Once t he vapor phase is select ed, t he liquid phase needs t o defined.
Act ivit y Model Specificat ions
The Act ivit y Models perform calculat ions for t he liquid phase only. Once
a Liquid phase model is select ed, t he model opt ions group is filled wit h
propert y met hods. The UNI QUAC act ivit y model opt ions are shown
Fi gur e 2. 70
Met hods Descr i pt i on
Equat i on of
St at e
Wit h t his select ion, t he ent halpy, ent ropy, and Cp
calculat ion met hods cont ained wit hin t he Equat ion of
St at e are used.
Lee- Kesl er The Lee- Kesler met hod may be used for t he calculat ion of
ent halpies, ent ropies and Cp values. This opt ion result s in
a combined Propert y Model, employing t he appropriat e
equat ion of st at e for vapor- liquid equilibrium calculat ions
and t he Lee- Kesler equat ion for t he calculat ion of
ent halpies and ent ropies. This met hod yields comparable
result s t o UniSim Design st andard equat ions of st at e and
has ident ical ranges of applicabilit y.
Lee- Kesler ent halpies may be slight ly more accurat e for
heavy hydrocarbon syst ems, but require more comput er
resources because a separat e model must be solved.
2- 96
below.
Wit h most of t he act ivit y models, you have a choice for t he calculat ion
met hod for t he st andard Ln Fugacit y Poynt ing Corr ect ion. By default ,
t he ideal st andard Ln Fugacit y is set wit hout t he Poynt ing correct ion
and may be changed using t he drop- down list . The Poynt ing fact or uses
each component s molar volume ( liquid phase) in t he calculat ion of t he
overall compressibilit y fact or.
2. 5. 2 Paramet ers Tab
The informat ion and opt ions displayed on t he Paramet ers t ab is
dependent on t he select ion of t he Propert y Model. Propert y models
which requir e addit ional paramet ers are displayed here, while ot hers
are not . For example, t he Chein- Null act ivit y model requires paramet ers
t o specify alt ernat ive models for binary int eract ion paramet ers. The
Chien- Null propert y package is ment ioned in t his sect ion.
Chien Null
different act ivit y models on a binary by binary basis. On t he Paramet ers
t ab, you can specify alt ernat ive act ivit y models t o be used for each
component pair.
Binary Component Paramet ers
To view t he Chein- Null act ivit y models t able, CN must be select ed as
t he liquid phase model and t he I P Model Name on t he binary
coefficient s t ab. All component s in t he case, including hypot het icals are
Fi gur e 2. 71
To aid you in adding
cust omized propert ies t o
t he model opt ions group,
refer t o Wizards & Add-
I ns sect ion of t he
Uni Si m Ther mo
Ref er ence Gui de.
2- 97
list ed in t he t able as shown below:
The t able displays t he default propert y met hods pr ovided by UniSim
Thermo for each binary pair. The met hods are accessed by highlight ing
a cell and opening t he drop- down list . From t he list you can specify an
Act ivit y Model t hat UniSim Thermo uses for t he calculat ion of each
binary. I f Henry' s Law is applicable t o a component pair, UniSim Thermo
select s t his as t he default propert y met hod. When Henry' s Law is
select ed by UniSim Design, you cannot modify t he model for t he binary
pair.
By default , t he Henry and NRTL act ivit y models are select ed for t he
binary pairs in t he above view. You may use t he default select ions, or
set t he propert y package for each binary pair. Remember t hat t he
select ed met hod appears in bot h cells represent ing t hat binary.
UniSim Thermo may filt er t he list of opt ions according t o t he
component s involved in t he binary pair.
2. 5. 3 Binary Coefficient s Tab
The Binary Coefficient s ( Binary Coeffs) t ab cont ains a t able which list s
t he int eract ion paramet ers for each component pair. Depending on t he
propert y met hod select ed, different est imat ion met hods are available
and t herefore a different view may be displayed.
All known binary int eract ion paramet ers are shown and t he unknown
int eract ion paramet ers are displayed wit h dashes ( - - - ) . When you exit
t he Basis Manager, unknown int eract ion paramet ers are set t o zero. You
have t he opt ion of overwrit ing any library int eract ion paramet er values.
For all t ables on t he Binary Coeffs t ab, t he horizont al component s
Fi gur e 2. 72
The Act ivit y Models
available in t he drop-
down list are:
None Required
Henry
van Laar
Margules
NRTL
Scat chard
Reg Soln
General
2- 98
across t he t op of t he t able represent t he " i" component and t he vert ical
component s represent t he " j " component .
Equat ion of St at e I nt eract ion Paramet er
( I P)
When you select an EOS model using t he I P Model Name drop- down
list , t he I nt eract ion Paramet er model informat ion is displayed on t he
Binary Coeffs t ab as shown in t he figure below.
The view cont ains a t able of cells commonly r eferred t o as t he Mat rix
Pane displaying binary int eract ion coefficient s. The t op of t he view
cont ains t he I P Model Name and Coefficient s drop- down list s. The dr op-
down list s det ermine which binary it eract ion coefficient s are shown in
t he t able:
Fi gur e 2. 73
Dr op- Dow n Li st Descr i pt i on
I P Model Name This drop- down list shows all of t he binary int eract ion
coefficient mat rices associat ed wit h t he propert y
package select ed. Ordinarily t here is one, t wo, or t hree
binary int eract ion coefficient mat rices per propert y
package. Equat ions of st at e t ypically have one mat rix,
and act ivit y coefficient models t ypically have t wo I P
mat rices, one for ordinary condensable component s
and t he ot her for non- condensible component s The
select ed Model is displayed in t he Mat rix Pane.
Coef f i ci ent s This drop- down list shows t he t ype of binary
int eract ion coefficient s t hat are displayed in t he Mat rix
Pane. The naming convent ion for each binary
int eract ion coefficient t ype is A1
i, j
, A2
i, j
, and so on.
This resembles t he " a
ij
", "b
ij
" form where i and j are
t he column and row in t he binary int eract ion coefficient
mat rix, respect ively.
Reset COM
Par amet er s
This but t on reset s all binary int eract ion coefficient s in
t he mat rix pane t o t he original UniSim Design
est imat ed paramet ers.
t o t he following Propert y
Models:
Kabadi Danner
Lee- Kesler Plocker
PR
PRSV
Soave Redlich
Kwong, SRK
Sour PR
Virial
Zudkevit ch Joffee
These t wo radio but t ons only appear for t he
PR and SRK based Equat ions of St at e.
This is equivalent
t o no K
ij
2- 99
The list of opt ions for bot h t he Model Name and Coefficient s are
dependent on t he propert y model ( EOS and Act ivit y) select ed for t he
vapor and liquid phase. For example, if you select t he Virial EOS as t he
vapor model, it appears in t he I P Model Name drop- down list . You can
view and/ or edit t he vir ial coefficient s for each binary. The following I P
model list represent s t he vapor ( Virial) and liquid models ( Chien- Null)
chosen for t he example.
Values are only shown in t he mat rix when t he Virial Vapor Phase model
is select ed on t he Set Up t ab. You can use t he default values suggest ed
by UniSim Design or edit t hese values. Virial coefficient s for t he pure
species are shown along t he diagonal of t he mat rix, while cross
coefficient s, which are mixt ure propert ies bet ween component s, ar e
t hose not along t he diagonal.
The numbers t hat appear in t he t able are init ially calculat ed by UniSim
Design and are modifiable. All known binary int eract ion paramet ers are
displayed, wit h unknowns displayed as dashes ( - - - ) . You have t he
opt ion of overwr it ing any library value.
For all Equat ion of St at e paramet ers ( except PRSV) , K
ij
= K
j i
. I f t he
value is modified for one of t he paramet ers, bot h cells of t he pair
aut omat ically updat e wit h t he same value. I n many cases, t he library
int eract ion paramet ers for PRSV do have K
ij
= K
j i
, but UniSim Design
does not force t his if you modify one paramet er in a binary pair.
I f you are using PR, SRK or t he PR Sour EOS, t wo radio but t ons appear
below t he I nt eract ion paramet ers t able.
Max i mum Est i mat ed BI P f or HC box: The maximum value allowed
for BI P ofhydr ocarbon compounds dur ing package init ializat ion. I t is not
used unless a value is specified by t he user.
Mat r i x Pane cont ai ns a l i st of t he bi nar y i nt er act i on
coef f i ci ent s f or al l bi nar y component pai r s i n t he Fl ui d
Pack age. The nami ng conv ent i on i s as f ol l ow s:
i col umn
j r ow
Est i mat e HC- HC/
Set Non HC- HC t o
0. 0
This radio but t on is t he default select ion. UniSim
Design provides t he est imat es for t he int eract ion
paramet ers in t he t able, set t ing all nonhydrocarbon
pairs t o 0.
Set Al l t o 0. 0 When t his is select ed, UniSim Design set s all
int eract ion paramet er values in t he t able t o 0. 0.
=
=
Only available wit h PR
EOS.
2- 100
Act ivit y Model I nt eract ion Paramet ers
The I P act ivit y model displayed in t he I P Model drop- down list is t he
corresponding liquid phase model select ed on t he Set Up t ab. When you
select an Act ivit y Model in t he I P Model Name list , t he I nt eract ion
Paramet er model informat ion is displayed on t he Binary Coeffs t ab, as
shown in t he figure below.
The act ivit y models display t he appropriat e set of Coefficient s for each
component pair. For example, Chien- Null allows for 3 set s of coefficient s
for each component pair, where ( A1
i, j
= a
i,j
, A2
i,j
= b
i, j
and A3
i,j
= c
i,j
) .
Refer t o t he Uni Si m Ther mo Ref er ence Gui de for more informat ion.
The int eract ion paramet ers for each binary pair ar e displayed; unknown
values show as dashes ( - - - ) . You can overwrit e any value.
To display a different coefficient mat rix pane ( i. e., B
ij
= A2
i, j
) , select t he
appropriat e coefficient using t he drop- down list .
2. 5. 4 St abilit y Test Tab
The St abTest t ab allows you t o cont rol how phase st abilit y and flash
calculat ions are performed. I f you encount er sit uat ions where t he flash
fails or you are suspicious about t he result s, you can use t his opt ion t o
Fi gur e 2. 74
Fi gur e 2. 75
t o t he following liquid
propert y models:
Chien Null
General NRTL
Margules
NRTL
UNI QUAC
van Laar
Wilson
You may reset t he binary
paramet ers t o t heir
original library values by
clicking t he Reset COM
Par amet er s but t on.
UniSim Thermo is not
opt imized for dynamics
mode and may result in
performance issues if
used in dynamics mode.
2- 101
approach t he solut ion using a different scheme.
For mult i- phase fluids, t here exist mult iple false calculat ed solut ions. A
false solut ion exist s when convergence occur s for a lower number of
phases t han exist s in t he fluid. For example, wit h a t hree- phase fluid,
t here is t he correct t hree- phase solut ion, at least t hree false t wo- phase
solut ions and mult iple false single- phase solut ions. A maj or problem in
converging t he flash calculat ion is arriving at t he right solut ion wit hout
a pr ior knowledge of t he number of equilibrium phases.
UniSim Design init ially performs a t wo- phase flash, unless t here is
st rong evidence for t hree phases. The result ing phases are t hen t est ed
for t heir st abilit y. The St abTest view is shown in t he figure below.
Flash Set t ings
The following opt ions are available in t he Flash Set t ings t able:
Fi gur e 2. 76
Fl ash Set t i ngs Descr i pt i on of Set t i ng
Max i mumNo.
I t er at i ons
You can set t he maximum number of it erat ions execut ed
in t he flash calculat ions. The algorit hm t erminat es aft er it
reaches t he maximum number of it erat ions.
Absol ut e
Tol er ance
This is t he convergence t olerance of t he governing flash
equilibrium equat ions. I f t he equilibrium equat ion error is
less t han t he Absolut e Tolerance, t he flash algorit hm is
assumed t o have converged.
Rel at i ve
Tol er ance
I n addit ion t o t he above condit ion, if t he change in t he
error bet ween it erat ions is less t han t he Relat ive
Tolerance, t he flash is assumed t o have converged.
I gnor e
Composi t i on
This is used t o det ect convergence t o t he t rivial solut ion
( where t he composit ions in t he t wo phases are ident ical) .
I f t he differences in t he composit ions of t he t wo phases
are all less t han t he Trivial Composit ion Tolerance, t he
result is assumed t o be t rivial.
2- 102
St abilit y Test Paramet ers
The St abilit y Test Paramet ers group is described in t he following
sect ions.
Maximum Phases Allowed
You can specify t he maximum number of phases allowed. I f t he
maximum is set t o 2, t he st abilit y t est t erminat es aft er a 2- phase flash.
Occasionally, you may st ill get t hree phases, as t he algorit hm may
at t empt t o st art dir ect ly wit h t he 3- phase flash.
Not e t hat if t he t rue solut ion has t wo phases and t he maximum phases
allowed is set t o t wo, t here is st ill no guarant ee t hat t he correct solut ion
is reached. For inst ance, for binary mixt ur es ar ound t he azeot ropic
point , t he correct solut ion may be liquid- liquid equilibrium, but t he
algorit hm may incorrect ly converge t o vapor- liquid equilibrium.
The St abilit y scheme used is pr oposed by Michelson( 1980a) . I n t he
Met hod group, you can choose t he met hod for performing t he st abilit y
t est calculat ions by select ing one of t he radio but t ons:
To av oi d di scar di ng azeot r opi c r esul t s, t he
compr essi bi l i t y ( Z) f act or s f or t he t w o phases ar e
comput ed and compar ed i n t he case w her e t he t w o
phases i nv ol v ed ar e model l ed usi ng t he same Pr oper t y
Met hods ( Equat i on of St at e Met hods) .
None No st abilit y t est is performed.
Low Uses a default set of Phases/ Component s t o I nit iat e t he
St abilit y Test . The following met hods are used: Delet ed
Phase, Wilsons Equat ion and Component I nit iat ion
( Wat er) . Only t he wat er component ( if it is part of your
Fluid Package) is "int roduced".
Medi um I n addit ion t o t hose met hods used for t he Low met hod,
t he Average of Exist ing and I deal Gas met hods are also
included. As well, t he heaviest and t he light est
component s in t he fluid are "int roduced" using t he
Component I nit iat ion met hod.
Al l All Phase I nit iat ion met hods are ut ilized, and all
component s are int roduced using t he Component
I nit iat ion met hod.
2- 103
Secant Met hod Flash Set t ing
The Secant Met hod Flash Set t ing group is shown below.
The set t ings t hat are available for t he Secant Met hod Flash are shown
in t he following t able.
Phase Mole Fract ion Tolerance
The phase fract ion t olerance is used whenever a vapor fract ion is given
along wit h a t emperat ure or pressure for t he secant met hod flash.
UniSim Design guesses a t emperat ure or pressure depending on which
variable is required and pr edict s a new vapor fract ion. The calculat ion
t erminat es when t he vapor fract ion is wit hin t he t olerance range and
t he flash is converged.
Ent halpy Tolerance
Different combinat ions may be used t o flash. I f t he ent halpy is given,
one is required and predict s a new ent halpy unt il t he flash is converged
wit hin t he t olerance specified.
Fi gur e 2. 77
Temper at ur e &
Pr essur e Set t i ngs
Descr i pt i on
Def aul t The default or init ial value.
l ow _bound The lower or minimum bound for t he secant
met hod search.
up_bound The upper or maximum bound for t he secant
met hod search.
max I nc The maximum increment or init ial st ep size for t he
secant t emperat ure search. The logarit hm of
pressure is used as t he primary variable for t he
pressure search, t hus an init ial pressure mult iplier
is used as t he pressure increment .
t ol er ance The t olerance during t he secant t emperat ure and
pressure search. I t is used mainly by t he backup
flashes.
2- 104 Ref er ences
2- 104
Ent ropy Tolerance
Different combinat ions may be used t o flash. I f t he ent ropy is given,
one is required and predict s a new ent ropy unt il t he flash is converged
wit hin t he t olerance specified.
2. 5. 5 React ions Tab
The UniSim Thermo Rxns t ab is t he same as t he t radit ional UniSim
Design propert y view. See Sect i on 2. 4.6 - React i ons Tab.
2. 5. 6 Not es Tab
See t radit ional UniSim Design t hermodynamics Sect i on 2. 4.8 - Not es
Tab.
2. 6 References
1
Wong, D. S. H., Sandler, S. I ., A Theoret ically Correct Mixing Rule for Cubic
Equat ions of St at e, A. I . Ch. E. Journal, 38, No. 5, p. 671 ( 1992)
2
Twu, H. C. and Bulls, J. W., Viscosit y Blending Test ed, Hydrocarbon
Processing, April 1981.
3
Ely, J. F. and Hanley, H. J.M., "A Comput er Program for t he Predict ion of
Viscosit y and Thermal Conduct ivit y in Hydrocarbon Mixt ures", NBS
Technical Not e 1039.
Hy pot het i cal s 3- 1
3- 1
3 Hypot het icals
3.1 I nt r oduct i on ............. ........................................................... .......... 3
3.2 Hy po Manager ........... ........................................................... .......... 3
3.3 Addi ng a Hypot het i cal - Ex ampl e ......................................... .......... 5
3.3.1 Creat ing t he Et hanol Hypo. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 5
3.3.2 Hypo/ Library Component Comparison .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 9
3.4 Cr eat i ng a Hypo Gr oup ......................................................... .........11
3.4.1 Hypo Group View . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 11
3.4.2 Supplying Basic I nformat ion . .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 14
3.4.3 UNI FAC St ruct ure. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 19
3.5 Hy pot het i cal Component Pr oper t y Vi ew ............................... .........21
3.5.1 I D Tab .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 22
3.5.2 Crit ical Tab . .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 23
3.5.3 Point Tab ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 23
3.5.4 TDep Tab ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 26
3.6 Sol i d Hypot het i cal s ... ........................................................... .........28
3.6.1 I D Tab .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 28
3.6.2 Props Tab... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 29
3.6.3 Point Tab ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 30
3.6.4 TDep Tab ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 31
3.6.5 PSD Tab.. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 32
3.7 Cl oni ng Li br ar y Component s ................................................ .........33
3.7.1 Convert ing a Library Component t o a Hypo.. ... .. ... .. .. ... .. ... .. .. ... .. .. 34
3- 2
3.8 Hypo Cont r ol s ........... ........................................................... ........ 34
3. 8. 1 Viewing Groups.. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. . 35
3. 8. 2 Moving Hypos . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. . 35
3.9 Ref er ences ................ ........................................................... ........ 36
3- 3
UniSim Design allows you t o creat e non- library or Hypot het ical
component s from t he Hypo Manager. Hypot het ical component s can be
pure component s, defined mixt ures, undefined mixt ures, or solids. You
can also convert / clone UniSim Design library component s int o
Hypot het icals, which allow you t o modify t he library values.
The Hypo Manager is locat ed on t he Hypot het icals t ab of t he Simulat ion
Basis Manager.
A wide select ion of est imat ion met hods are pr ovided for t he various
Hypo groups ( hydrocarbons, alcohols, et c. ) t o ensure t he best
represent at ion of behaviour for t he Hypot het ical component in t he
simulat ion. I n addit ion, met hods are provided for est imat ing t he
int eract ion binaries bet ween hypot het icals and library component s. You
can also use Hypot het icals wit h t he Tabular Package, as well as in
React ions.
I n UniSim Design, Hypot het ical component s exist independent of t he
Fluid Package. When a Hypot het ical is creat ed, it is placed in a Hypo
Group. From t he Hypo Manager, you can creat e new Hypo Groups and
move Hypot het ical component s wit hin t he Hypo Groups. Hypo Gr oups
can also be import ed and export ed, t hus making t hem available t o any
simulat ion case.
Since Hypot het ical component s are not exclusively associat ed wit h a
part icular Fluid Package, it is possible for mult iple Fluid Packages t o
share Hypot het icals. I n ot her words, you only need t o creat e a
Hypot het ical once, and it can be used in any Fluid Package t hroughout
t he case.
3. 2 Hypo Manager
By select ing t he Hypot het icals t ab from t he Simulat ion Basis Manager,
3- 4 Hy po Manager
3- 4
t he following view appears:
The left side of t he view is t he Hypot het ical Groups group. This list s all
t he Hypot het ical groups current ly inst alled in t he simulat ion. The
available commands for t his group ( accessed using t he associat ed
but t ons) are as follows:
The right side of t he view displays t he Hypot het ical Quick Reference
group. This group includes all Hypot het icals current ly inst alled in t he
Basis Environment ( Hypo Name column) along wit h t heir associat ed
Hypo Groups ( Group Name column) . The available but t ons wit hin t his
Fi gur e 3. 1
You can I mpor t and Ex por t Hy pot het i cal gr oups, al l ow i ng
y ou t o use def i ned hy pot het i cal s i n any f ut ur e si mul at i on
Vi ew Accesses t he Hypo Group view for t he select ed group.
Add Adds a Hypot het ical Group t o t he present case.
Del et e Delet es t he select ed Hypot het ical Group from t he case.
Tr ansl ocat e Searches t hrough all of t he hypot het ical component s in t he
case and if t here are duplicat es UniSim Design replaces
t hem and put s all t he duplicat es in a separat e Hypo group
which t hen can be delet ed.
This is int ended for use when large cases have had large
numbers of t emplat es/ fluid packages import ed and t here
are lot s of repeat ed hypot het icals in t he case.
I mpor t I mport s a Hypot het ical Group from disk.
Ex por t Export s t he select ed Hypot het ical Group and saves it t o a
file, so t hat it can be ret rieved at a lat er t ime.
Hypot het ical groups and
individual hypot het ical
component s can be
inst alled in more t han
one Fluid Package.
3- 5
group are described below:
3. 3 Adding a Hypot het ical -
Example
I n t his example, a hypot het ical Et hanol component is defined, and t he
result s t o t he library Et hanol component using t he Wilson pr opert y
package are compared. The et hanol hypot het ical component is defined
as having a boiling point of 78. 25 C and a specific gravit y of 0. 789.
3. 3. 1 Creat ing t he Et hanol Hypo
To creat e a et hanol hypo, follow t he st eps out lined below:
1. Open a new case in UniSim Design.
2. Select Tool s | Pr ef er ences in t he menu bar t o open t he Session
Preferences view.
3. I n t he Session Preferences view, click t he Var i abl es t ab and select
t he Uni t s page.
4. Select SI as t he unit s for t his example case.
5. I n t he Simulat ion Basis Manager view, select t he Hy pot het i cal s
t ab.
6. From t he Hypot het ical Groups group, click t he Add but t on t o creat e
a new Hypot het ical Group. UniSim Design aut omat ically names t his
group Hy poGr oup1. You can change t he name lat er, if desired.
Vi ew Hy po Access t he propert y view for t he highlight ed Hypot het ical.
Vi ew Gr oup Access t he Hypo Group view for t he highlight ed
Hypot het ical.
Move Hy pos Move Hypot het icals from one Hypo Group t o anot her.
Cl one Comps Use a copy of a select ed library component s as t he basis for
defining a Hypot het ical.
You must inst all a
Hypot het ical Group before
you can inst all a Hypo
component .
3- 6 Addi ng a Hy pot het i cal - Ex ampl e
3- 6
7. When you add a new Hypot het ical Group, UniSim Design
aut omat ically opens t he Hypo Group view, where you add and
define t he Hypot het ical component ( s) for t he group. On t his view,
ent er Hy poAl cohol as t he new Group Name.
Not ice t hat t he UniSim Design default in t he Component Cl ass list
is Hydr ocarbon.
8. I n t he Component Cl ass drop- down list , select Al cohol .
9. Now, inst all a Hypot het ical component . From t he I ndi v i dual Hy po
Cont r ol s group, click t he Add Hy po but t on. This adds a
Hypot het ical component and aut omat ically names it Hy po20000* .
10. Ent er a new name for t his component by select ing t he Name cell
t yping Hy poEt oh.
11. I n t he NBP cell, ent er t he normal boiling point of t he component as
78.25C.
12. The specific gravit y for t he hypot het ical component is 0. 789. I n t he
Li q Densi t y cell, ent er 0.789 and select t he SG_60/ 60api unit s.
A liquid densit y of 787. 41 kg/ m
3
is calculat ed by UniSim Design.
Fi gur e 3. 2
Fi gur e 3. 3
3- 7
13. Alt hough UniSim Design could est imat e t he unknown propert ies for
HypoEt oh wit h only t he NBP and Liquid Densit y, more accurat e
result s are obt ained if t he component st ruct ure is supplied. Click t he
UNI FAC but t on t o access t he UNI FAC Component Bui l der.
14. The chemical formula of et hanol is C
2
H
5
OH, and it is compr ised of
t he groups CH
3
, CH
2
, and OH. Highlight CH3 in t he Av ai l abl e
UNI FAC Gr oups list . I t is t he first select ion in t he list .
15. Click t he Add Gr oup( s) but t on.
Not ice t hat a 1 is displayed under Sub Group in t he UNI FAC
St r uct ur e group. By default , UniSim Design assigns t he value 1
t o t he How Many cell. The number is valid, since t his is t he number
of CH
3
groups requir ed. The number of Free Bonds has increased t o
1 wit h t he addit ion of t he CH3 Sub Group.
16. To add t he CH
2
group, highlight it in t he Av ai l abl e UNI FAC
Gr oups list ( it is t he second in t he list ) and click t he Add Gr oup( s)
but t on. Again, only 1 Sub Group is required, so t he default is
accept able.
Fi gur e 3. 4
3- 8
17. Since t he OH group is not immediat ely visible in t he list of
Av ai l abl e UNI FAC Gr oups, a different approach is t aken. I n t he
UNI FAC St r uct ur e input field, t ype OH at t he end of t he exist ing
st ruct ure ( CH3CH2) and pr ess ENTER.
18. Once t he UNI FAC St ruct ure is complet e, UniSim Design calculat es
t he UNI FAC Base and Cr it ical Proper t ies. Click t he Cl ose icon t o
close t he view and ret urn t o t he Hypo Group view.
UniSim Design can now use t he exist ing informat ion ( NBP, Liquid
Densit y and UNI FAC st ruct ure) t o est imat e t he remaining propert ies
for t he Hypot het ical component .
19. We will now examine t he Est imat ion Met hod t hat UniSim Design
uses. Click t he Est i mat i on Met hods but t on t o access t he Propert y
Est imat ion view.
20. I f you want , you can change t he est imat ion met hod for any
propert y. I n t his example, all propert ies use t he Default Met hod.
Click t he Cl ose icon t o ret urn t o t he Hypo Group view.
Fi gur e 3. 5
Fi gur e 3. 6
Not ice t hat t he
I ncompl et e st at us
message is replaced wit h
Compl et e when t here
are 0 Free Bonds.
Propert y Est imat ion
Met hods are explained in
Sect i on 3.4. 2 -
Suppl y i ng Basi c
I nf or mat i on.
3- 9
21. Click t he Est i mat e Unk now n Pr ops but t on and UniSim Design
uses t he current ly specified met hods t o est imat e t he unknown
propert ies for t he component . The molecular weight for t he
hypot het ical is t he same as t he molecular weight for et hanol, 46. 07,
since t he UNI FAC st ruct ur e is used for t he Hypo component .
22. You can examine all propert ies for t he Hypo t hrough it s propert y
view. Double- click on t he Hypot het ical component name,
Hy poEt oh, t o access t he Component propert y view.
23. Click t he Cl ose icon t o ret urn t o t he Hypo Group view.
24. Click t he Cl ose icon and UniSim Design r et urns you t o t he
Hypot het icals t ab of t he Simulat ion Basis Manager. The Et hanol
Hypot het ical has is creat ed.
3. 3. 2 Hypo/ Library Component
Comparison
To conclude, compare t he et hanol hypot het ical t o t he et hanol library
component . Go t o t he Simulat ion Basis Manager:
1. On t he Fl ui d Pk gs t ab, click t he Add but t on t o inst all t he new Fluid
Fi gur e 3. 7
Fi gur e 3. 8
Remember t hat specified
values are displayed in
blue, and UniSim Design
est imat ed values are
displayed in red.
For furt her informat ion
regarding t he Propert y
View, refer t o Sect i on
3. 5 - Hypot het i cal
Component Pr oper t y
Vi ew .
3- 10
Package.
2. On t he Set Up t ab, select Wi l son as t he Propert y Package and
close t he fluid package view.
3. Move t o t he Component s t ab and add Et hanol t o t he Select ed
Component List by highlight ing t he Library Component s page in t he
Add Component group.
4. From t he Available Hypo Component s group, highlight t he
Hy poEt oh* component and click t he Add Hy po but t on from t he
Hypot het ical page.
5. Move t o t he Bi nar y Coef f s t ab in t he fluid package propert y view
and click t he Unk now ns Onl y but t on in t he Coeff Est imat ion group.
6. Close t he Fluid Package proper t y view.
7. Click t he Ret ur n t o Si mul at i on Env i r onment but t on t o ent er t he
Main Envir onment .
8. I n t he Workbook, creat e t he st r eam Pur e. Ent er a vapour fract ion of
0 and a pr essure of 1 at m for t he st ream on t he Mat erial St r eams
t ab of t he workbook. Move t o t he Composit ions t ab an ent er 1 for
t he mole fract ion of Et hanol, and 0 for HypoEt oh* .
9. Now creat e a second st ream, Hy po. Ent er a vapour fract ion of 0
and a pr essure of 1 at m for t he st ream. The mole fract ion of
Hy poEt oh* is 1, and t hat for Et hanol is 0.
When you have specified t hese t wo st reams, UniSim Design
calculat es t he bubble point t emperat ure for each st ream. The
Condit ions t ab of t he propert y view for each st ream is shown below.
Fi gur e 3. 9
3- 11
3. 4 Creat ing a Hypo Group
When defining a hypot het ical, t here is no set procedure. The following
is a suggest ed sequence in which you can follow:
1. Creat e t he Hypo Group. For more informat ion, see Sect i on 3.4.1 -
Hy po Gr oup Vi ew .
2. Select t he Component Class for t he Hypo Group. For more
informat ion, see Sect i on 3. 4. 1 - Hy po Gr oup Vi ew .
3. Set t he Est imat ion Met hods for t he Group ( opt ional) . For more
informat ion, see Sect i on 3. 4. 2 - Suppl y i ng Basi c I nf or mat i on.
4. I nst all t he Hypot het icals.
5. Supply all informat ion t hat you have for t he Hypo. For more
informat ion, see Sect i on 3. 4. 2 - Suppl y i ng Basi c I nf or mat i on.
6. Supply a UNI FAC st ruct ure for t he Hypo ( opt ional) . For more
informat ion, see Sect i on 3. 4. 3 - UNI FAC St r uct ur e.
7. Est imat e t he Propert ies for t he Hypo.
3. 4. 1 Hypo Group View
As ment ioned in t he Hypot het ical example, you add a Hypo Group by
clicking t he Add but t on from t he Hypot het icals t ab of t he Simulat ion
Basis Manager. This opens t he Hypo Group view, which cont ains t wo
groups, ( Hypo Group Cont rols and I ndividual Hypo Cont rols) , and a
t able of est imat ed or known pr opert y values.
Fi gur e 3. 10
3- 12 Cr eat i ng a Hy po Gr oup
3- 12
Hypo Group Cont rols
The Hypo group cont ains t he following opt ions:
I ndividual Hypo Cont rols
The I ndividual Hypo Cont rols group at t he bot t om of t he Hypo Group
view cont ains but t ons for manipulat ing t he Hypot het icals wit hin t he
Hypo Group and t wo radio but t ons for swit ching bet ween Base
Gr oup Name Displays t he current name for t he Hypot het ical Group.
UniSim Design provides a default name, but you can
change t his t o a more descript ive name. I ndividual
Hypot het ical component s must reside inside of a
Hypot het ical group.
Component
Cl ass
Every component in a Hypo Group must be of a common
Component Class. The opt ions are accessed using t he drop-
down list at t ached t o t he input cell. There is a wide
select ion of available Classes, which allows for bet t er
est imat ion of t he component propert ies. UniSim Design, by
default , select s t he Component Class t o be Hydrocarbon.
Prior t o inst alling any component s, select t he Component
Class.
Est i mat i on
Met hods
Accesses t he Propert y Est imat ion view, from which you can
select an est imat ion met hod for each propert y. The
select ed est imat ion met hods apply t o all Hypot het icals in
t he Hypo Group.
Est i mat e
Unk now n
Pr ops
This but t on est imat es t he unknown propert ies for all
Hypot het ical component s wit hin t he Hypo Group, using t he
met hods chosen on t he Propert y Est imat ion view. For more
informat ion, Sect i on 3.4. 2 - Suppl y i ng Basi c
I nf or mat i on.
Cl one Li br ar y
Comps
UniSim Design allows you t o convert library component s
int o hypot het ical component s. For more informat ion, see
Sect i on 3. 7 - Cl oni ng Li br ar y Component s.
Not es Allows you t o supply Not es and Descript ions for t he
Hypot het ical Group. This is useful when export ing Hypo
groups, because when you import t hem lat er, t he
descript ion appears along wit h t he Hypo group name.
For t he Component Cl ass, t her e ar e var yi ng l evel s of
speci f i ci t y. For ex ampl e, under Al cohol , y ou can speci f y sub-
cl asses of al cohol s, such as Al i phat i c, Ar omat i c, Cy cl o and
Pol y . Usi ng a st r i ct er degr ee of component t y pe assi st s
Uni Si m Desi gn i n choosi ng appr opr i at e est i mat i on met hods;
how ever , i t f or ces al l component s t o be cal cul at ed usi ng t he
same met hod. I f y ou w ant t o mi x component cl asses ( i .e.,
bot h Al i phat i c and Ar omat i c i nsi de t he same Hy po Gr oup) ,
sel ect t he mor e gener al Component Cl ass of Al cohol .
3- 13
Propert ies and Vapour Pressure dat a.
The t able displayed in t he middle sect ion of t he Hypo Group view,
displays eit her t he Base Propert ies or t he Vapour Pressure propert ies,
depending on which radio but t on is select ed. You can add a new Hypo
component in eit her t he Base Propert ies or Vapour Pressure view.
Base Propert ies
The Base Pr opert ies for each Hypot het ical are shown on t he Hypo
Group view when t he Base Propert ies radio but t on is select ed.
The t able list s each Hypot het ical along wit h t he following Base
Propert ies:
Vi ew Displays t he Propert y View for t he highlight ed hypot het ical
component .
Add Hypo Aut omat ically adds a new hypot het ical component t o t he
group. UniSim Design places t he new Hypo in t he t able,
and names it according t o t he default naming convent ion
( set in t he Session Preferences) .
Add Sol i d Aut omat ically adds a new solid hypot het ical component t o
t he group. UniSim Design places t he new Hypo in t he t able,
and names it according t o t he default naming convent ion
( set in t he Session Preferences) .
Del et e Delet es t he highlight ed hypot het ical component from t he
case. Aft er delet ing a Hypo it cannot be recovered.
UNI FAC Opens t he UNI FAC Component Builder, from which you can
provide t he UNI FAC St ruct ure for t he highlight ed
hypot het ical component .
Fi gur e 3. 11
Base Pr oper t y Descr i pt i on
NBP Normal boiling point
MW Molecular weight
The View, Delet e, and
UNI FAC but t ons will not
be available unless a
hypot het ical is present
in t he case.
These propert ies are t he
same as t hose shown on
t he Cr i t i cal t ab of t he
Hypo component
propert y view.
3- 14
The Base Pr opert y Li q Densi t y represent s t he Hypo Component ' s
densit y at 60F. I t will normally be specified by user in kg/ m3, and it also
can be replaced by ot her specific gravit ies, such as SG60/ 60api,
SG_H2O60nbs and SG_H2O4 which mean t he conversion fact ors
bet ween component liquid densit y and wat er densit y at different
t emperat ure or st andard. The specific gravit ies SG60/ 60api and
SG_H2O60nbs were defined as t he rat io of t he component liquid
densit y at 60F t o t he wat er densit y at 60F in API st andard and NBS
( now changed t o NI ST) st andard respect ively, while SG_H2O4 was
defined as t he rat io of t he component liquid densit y at 60F t o t he wat er
densit y at 4C.
Vapour Pressure Propert ies
The Vapour Pressure t able displays t he t emperat ur e range and Ant oine
Coefficient s for t he hypot het ical component s. Also shown are t he
pressure and t emperat ure unit s on which t he equat ion is based and t he
form of t he equat ion.
3. 4. 2 Supplying Basic I nformat ion
Before UniSim Design can est imat e t he pr opert ies for a hypot het ical,
some informat ion about t he Hypo must be provided. For t he est imat ion,
you must supply a minimum amount of informat ion and select t he
Li q Densi t y Liquid densit y
Tc Crit ical t emperat ure
Pc Crit ical pressure
Vc Crit ical volume
Acent r i ci t y Acent ric fact or
Fi gur e 3. 12
Base Pr oper t y Descr i pt i on
I ndividual Base
Propert ies are supplied
by select ing t he
appropriat e cell. Use t he
drop- down list t o select
t he unit s wit hin t he cell.
The values shown on t his
view are also available on
t he TDep t ab of t he
individual Hypo propert y
view.
Use t he horizont al scroll
bar t o view Coeff E and
Coeff F.
3- 15
est imat ion met hods t o be used.
Minimum I nformat ion Required
I f t he hypot het ical component is defined as a hydrocarbon, t he
appropriat e default correlat ions can be used t o calculat e it s crit ical
propert ies or any ot her missing informat ion. I t s int eract ion paramet ers
are also calculat ed by UniSim Design based on t he est imat ed crit ical
propert ies. For UniSim Design t o est imat e t he component ' s crit ical
propert ies, a minimum amount of informat ion must be supplied, as
shown in t he following t able.
Est imat ion Met hods
Prior t o inst alling any Hypot het icals int o a Hypo gr oup, examine t he
Est imat ion Met hods which UniSim Design uses t o calculat e t he
unknown propert ies for a hypot het ical component . You can specify a
est imat ion met hod for each pr opert y. Click t he Est imat ion Met hods
but t on on t he Hypo Group view.
The Est imat ion Met hods t hat you choose for t he Hypo Group apply t o all
Hypot het icals in t hat group.
There ar e t hree groups in t he Propert y Est imat ion view and are
Nor mal Boi l i ng Poi nt Mi ni mum Requi r ed I nf or mat i on
< 700 F ( 370 C) Boiling Point
> 700 F ( 370 C) Boiling Point and Liquid Densit y
Unknown Liquid Densit y & Molecular Weight
Fi gur e 3. 13
The more informat ion
you can supply, t he more
accurat e t he est imat ions
are.
3- 16
described below:
The following t able individually list s each Propert y, it s Default Met hod,
it s Available Est imat ion Met hods and t he Variables Affect ed by
est imat ing t he Propert y. I t is underst ood t hat each propert y can have
Do Not Est imat e select ed as it s Est imat ion Met hod, so t his opt ion does
not appear in t he Available Met hods list .
Gr oup Descr i pt i on Vi ew
Pr oper t y t o Set
Met hods For
This group list s all t he available
propert ies. From t he list , choose t he
propert y for which you want t o set t he
Est imat ion Met hod. Use t he scroll bar t o
move t hrough t he list . I nit ially, UniSim
Design set s all t he propert ies t o t he
Default Met hod.
Est i mat i on
Met hod For
Sel ect ed
Pr oper t y
This drop- down list displays all t he
available est imat ion met hods for t he
highlight ed propert y. Depending on t he
propert y, t he drop- down list differs. The
list shown here is a part ial display of
est imat ion met hods for Crit ical
Temperat ure.
Var i abl es
Af f ect ed by t hi s
Est i mat e
This group list s all t he variables t hat are
affect ed by t he select ed est imat ion
met hod. The list changes depending on
t he propert y select ed. For example, when
you select an est imat ion met hod for
Crit ical Temperat ure, you are not only
affect ing t he crit ical t emperat ure, but
also t he propert ies which use crit ical
t emperat ure in t heir est imat ion or
calculat ion.
Pr oper t y Def aul t Met hod Av ai l abl e Met hods Var i abl es Af f ect ed
Cr i t i cal
Temper at ur e
if
LI Q
> 1076 kg/ m
3
or
NBP > 800 K, Lee-
Kesl er is used
NBP < 548. 16 K and
LI Q
< 850 kg/ m
3
,
Ber gman is used
all ot her cases, Cav et t
is used
Aspen, Bergman, Cavet t ,
Chen Hu, Eat on Port er,
Edmist er, Group
Cont ribut ion, Lee Kesler,
Mat hur, Meissner Redding,
Nokay, Riazi Dauber, Roess,
PennSt at e, St anding, Twu
Crit ical
Temperat ure
St andard Liquid
Densit y
COSTALD
Variables
Viscosit y Thet as
Cr i t i cal
Pr essur e
if
LI Q
> 1076 kg/ m
3
or
NBP > 800 K, Lee-
Kesl er is used
NBP < 548. 16 K and
LI Q
< 850 kg/ m
3
,
Ber gman is used
is used
Aspen, Bergman, Cavet t ,
Edmist er, Group
Cont ribut ion, Lee Kesler,
Lydersen, Mat hur,
PennSt at e, Riazi Daubert ,
Rowe, St anding, Twu
Crit ical Pressure
St andard Liquid
Densit y
COSTALD
Variables
Viscosit y Thet as
3- 17
Cr i t i cal
Vol ume
if all mehods are set as
default , Honeyw el l
pr opr i et ar y is used
in all ot her cases,
Pi t zer is used
Group Cont ribut ion, Pit zer,
Twu
Crit ical Volume
St andard Liquid
Densit y
COSTALD
Variables
Viscosit y Thet as
Acent r i ci t y if all met hods are set as
default
if solid, Lee- Kesl er is
used
if NBP/ and
NBP> 800K, Lee
Kesl er is used
kg/ m
3
or
NBP> 800 K, Lee
Kesl er is used

and
< 850 kg/ m
3
,
Ber gman is used
is used
else
Lee Kesl er is used
Bergman, Edmist er, Lee
Kesler, Pit zer, Pit zer Curl,
Robinson Peng, Twu
w
e
Gs
St andard Liquid
Densit y
COSTALD
Variables
Viscosit y Thet as
Mol ecul ar
Wei ght
if NBP < 155 F,
Ber gman is used
if Lee-
Kesl er is used
API , Aspen, Aspen Least q,
Bergman, Hariu Sage, Kat z
Firoozabadi, Kat z Nokay,
Lee Kesler, PennSt at e, Riazi
Daubert , Robinson Peng,
Twu, Whit son, Chung
Modified Twu, API 2B21
Molecular Weight
Nor mal
Boi l i ng Poi nt
Honey w el l
pr opr i et ar y
API 2B21 Normal Boiling
Point
Viscosit y Thet as
Vapour
Pr essur e
for Hydrocarbon, Lee-
Kesl er is used
all ot her cases, Ri edel
is used
Gomez Thodos, Lee Kesler Ant oine
Coefficient
PRSV_Kappa
Li qui d
Densi t y
if NBP < 155 F,
Ber gman is used
if Kat z
Fi r oozabadi is used
Bergman, BergmanPNA,
Chueh Prausnit z, Gunn
Yamada, Hariu Sage, Kat z
Firuzabadi, Lee Kesler, Twu,
Whit son, Yarborough, Yen
Woods
St andard liquid
Densit y
COSTALD
Variables
I deal Gas
Ent hal py
Cavet t Cavet t , Falon Wat son,
Group Cont ribut ion, Lee
Kesler, Modified Lee Kesler,
I deal H Coefficient
Heat of
For mat i on
Honey w el l
pr opr i et ar y
Group Cont ribut ion Heat of Format ion
Heat of
Combust ion
I deal Gas
Gi bbs Ener gy
Honey w el l
pr opr i et ar y
Group Cont ribut ion Gibbs Coefficient
Heat of
Vapour i zat i o
n
Tw o Ref er ence Fl ui d
( using benzene and
carbazole)
Chen, Pit zer, Riedel, Two
Reference
1
, Vet ere
Cavet t Variables
T
c
0.8 >
LIQ
1076 >
NBP 548.15K s
LIQ
NBP 155F >
NBP 155F >
3- 18
I n defining Hypot het ical component s, t here are some propert ies for
which you cannot select t he est imat ion met hod. UniSim Design
det ermines t he proper met hod based on informat ion you have
provided. The following t able list s t hese propert ies and t heir respect ive
default met hods:
Li qui d
Vi scosi t y
for non- Hydorcarbon
or NBP < 270 K
Let sou St i el is used
for Hydorcarbon and
NBP < 335 K, NBS
vi scosi t y is used
all ot her cases, Tw u is
used
Honeywell Propriet ary,
Let sou St iel
Viscosit y Thet as
Sur f ace
Tensi on
Brock Bird Brock Bird, Gray, Hankin,
Sprow Prausnit z
Tabular Variables
Radi us of
Gy r at i on
Honey w el l
pr opr i et ar y
Default Only Crit ical
Temperat ure
Crit ical Pressure
Normal Boiling
Point
Molecular Weight
St andard Liquid
Densit y
Pr oper t y Def aul t Est i mat i on Met hod
Li qui d Ent hal py The previously calculat ed Li qui d Heat
Capaci t y is used.
Vapour Ent hal py Liquid Ent halpy + Ent halpy of Vapourizat ion
Chao Seader Mol ar
Vol ume
I f T
c
> 300 K, Mol ar Vol ume f r om
COSTALD @ 25 C and 1 at m is used
all ot her cases,
LI Q
@ 60 F is used
Chao Seader
Acent r i ci t y
component acent r i c f act or is used
Chao Seader
Sol ubi l i t y Par amet er
I f T
c
> 300K, Wat son t y pe Ent hal py of
Vapor i zat i on is used
all ot her cases, val ues of 5. 0 are used
Cav et t Par amet er Tw o Ref er ence Fl ui d
1
met hod ( using
benzene and carbazole)
Di pol e Moment No est imat ion met hod available, set s value
equal t o zero.
Ent hal py of
Combust i on
No est imat ion met hod available, set s value t o
< empt y> .
COSTALD
Char act er i st i c
Vol ume
I f NBP < 155 F, Ber gman is used
all ot her cases, Kat z- Fi r oozabadi is used
Li qui d Vi scosi t y
Coef f i ci ent s A and B
For non- Hydrocarbon or NBP < 270 K,
Let sou St i el is used
for Hydrocarbon and NBP < 335 K, NBS
v i scosi t y is used
all ot her cases, Tw u is used.
Vapour Vi scosi t y Chung
PRSV Kappa1 Vapour Pr essur e f r om Ant oi ne s
Equat i on
Kf act or 1 Vapour Pr essur e f r om Ant oi ne s
Equat i on
3- 19
3. 4. 3 UNI FAC St ruct ure
Most of t he est imat ion met hods require a UNI FAC st ruct ure for some
aspect of t he est imat ion. I t may be t hat eit her t he pr opert y it self, or
some ot her propert y t hat is affect ed by t he est imat ion procedure
requires t he chemical st ruct ure.
The UNI FAC st ruct ure is supplied t hrough t he UNI FAC Component
Builder. This can eit her be accessed by clicking t he UNI FAC but t on in
t he Hypo Group view, or by clicking t he St ruct ur e Builder but t on on t he
I D t ab of t he Hypot het ical component propert y view. Whichever rout e is
t aken, t he following view is displayed:
The UNI FAC Component Builder view is made up of t he following
obj ect s:
Fi gur e 3. 14
Obj ect s Descr i pt i on
UNI FAC St r uct ur e
Gr oup
Displays t he Type and Number of Sub Groups in
t he UNI FAC St ruct ure.
Add Gr oup( s) Adds t he current ly select ed Sub Group from t he
Available UNI FAC Groups list box t o t he UNI FAC
St ruct ure group.
Del et e Gr oup Delet es t he current ly select ed Sub Group in t he
UNI FAC St ruct ure group.
Fr ee Bonds Displays t he number of free bonds available in t he
present UNI FAC St ruct ure. This is 0 when t he
st ruct ure is complet e.
St at us Bar This bar is found in t he cent re of t he view. I t
indicat es t he present st at us of t he UNI FAC
St ruct ure. You see eit her I ncomplet e in red,
Complet e in green, or Mult i- Molecules in yellow.
Av ai l abl e UNI FAC
Gr oups
Cont ains all t he available UNI FAC component sub
groups.
UNI FAC St r uct ur e
f i el d
Displays t he chemical st ruct ure of t he molecule
you are building.
This sect ion makes
reference t o bot h t he
UNI FAC St ruct ure group
( t he t able of cells) and
t he UNI FAC St ruct ure
ent ry field.
3- 20
The procedure for supplying t he UNI FAC st ruct ure is t o highlight t he
Sub Group( s) in t he Available UNI FAC Groups column and select t he
Add Group( s) but t on. Addit ional sub groups can be accessed in t he list
by using t he Scroll Bar.
As you add sub groups, UniSim Design displays t he number of Free
Bonds available. This is zer o when t he UNI FAC st ruct ur e is complet e.
When you have supplied enough groups t o sat isfy t he bond st ruct ure,
t he st at us message changes t o Complet e ( wit h a green background) .
As you specify groups, t he UNI FAC Calculat ed Base Propert ies and
UNI FAC Calculat ed Crit ical Propert ies are aut omat ically updat ed based
on t he new st ruct ure.
There are t hree met hods available for adding Sub Groups t o t he UNI FAC
St ruct ure:
UNI FAC Cal cul at ed
Base Pr oper t i es
Displays propert ies such as Molecular Weight , t he
UNQUAC R paramet er, and t he UNI QUAC Q
paramet er for a UNI FAC St ruct ure wit h at least 1
sub group.
UNI FAC Cal cul at ed
Cr i t i cal Pr oper t i es
Displays t he crit ical propert ies for a UNI FAC
St ruct ure wit h at least 1 sub group.
Sub Gr oup Descr i pt i on
Hi ghl i ght i ng
t he Sub
Gr oup
The list of Available UNI FAC Groups displays all t he sub
groups. Not ice t hat CH
3
is t he first select ion in t his list . You
can use t he scroll bars t o move t hrough t he list unt il you
find t he group you need. When you find t he correct Sub
Group, highlight it , and click t he Add Gr oup( s) but t on.
The sub group now appears in t he UNI FAC St ruct ure group.
Usi ng t he
Sub Gr oup
Number
Each sub group has a number associat ed wit h it . I f you
know t he number for t he sub group you want t o add t o t he
UNI FAC St ruct ure, move t he act ive locat ion t o t he Sub
Group column of t he UNI FAC St ruct ure group. Ent er t he
number of t he Sub Group. UniSim Design does not
aut omat ically fill in t he number of sub groups. Move t he
act ive locat ion t o t he How Many column and t ype in t he
number of sub groups required.
Ty pi ng i n t he
UNI FAC
St r uct ur e
i nput f i el d
Not ice t he UNI FAC St ruct ure input field near t he bot t om of
t he view. Any sub groups already inst alled are list ed here.
Place t he cursor aft er t he last group, and t ype in t he group
t o inst all. For example, if we want t o add an OH group, t ype
in OH. When you t ype t he sub group in t his box, UniSim
Design aut omat ically adds it t o t he UNI FAC St ruct ure
group.
You can add mul t i pl es of a Sub Gr oup i n t he UNI FAC
St r uct ur e box . Ty pe t he number of Sub Gr oups and t he Sub
Gr oup name, separ at ed by a space. For ex ampl e, t y pe 3 CH2
t o add t hr ee CH2 gr oups t o t he UNI FAC st r uct ur e. NOTE: You
cannot add Sub Gr oups i n t hi s w ay t o an ex i st i ng UNI FAC
st r uct ur e.
Obj ect s Descr i pt i on
You can highlight more
t han one sub group, and
add all at t he same t ime.
Not ice t he difference
bet ween t he UNI FAC
St ruct ure group ( t he
t able of cells) and t he
UNI FAC St ruct ure ent ry
field.
3- 21
UniSim Design aut omat ically calculat es Base Propert ies and Crit ical
Propert ies using t he current ly supplied st ruct ure.
3. 5 Hypot het ical Component
Propert y View
Hypot het icals, like library component s, have t heir own propert y view.
Once inside, you can add or modify informat ion, or examine t he result s
of t he est imat ions.
You can access t he propert y view for t he Hypo component from
different views:
The Hypot het ical propert y view is made up of five t abs and are shown
below. Some of t he t abs have radio but t ons for swit ching bet ween t he
various propert ies. When a different radio but t on is select ed, UniSim
Design redraws t he view wit h t he informat ion appropriat e t o t he it em.
Vi ew Met hod of Accessi ng Hy po
Manager ,
Hy pot het i cal s Tab
All t he hypot het ical component s are displayed in
t he Hypot het ical Quick Reference group. You can
eit her double- click on t he component name, or
highlight it and click t he Vi ew Hypo but t on.
Hy po Gr oup All t he hypot het ical component s in t he Hypo Group
you have chosen t o view, are displayed. Eit her
double- click on t he Hypo component you want t o
view, or highlight it and click t he Vi ew but t on.
Manager ,
Component s Tab
Aft er adding a hypot het ical t o t he Select ed
Component List group, highlight it and click t he
Vi ew Component but t on or obj ect inspect it s
name and select Vi ew .
Fi gur e 3. 15
3- 22 Hy pot het i cal Component Pr oper t y
3- 22
Aft er you have ent ered adequat e est imat ion paramet ers, you can click
t he Est imat e Unknown Propert ies but t on t o complet e t he hypot het ical
est imat ion. The Edit Propert ies but t on allows you t o edit propert ies
wit hin t he hypocomponent at t he component level. The Edit Visc Curve
but t on allows you t o recalculat e t he viscosit y coefficient s based on t he
t emperat ure and dynamic viscosit y dat a provided by t he user. Refer t o
Edi t Pr oper t i es in Sect i on 1. 2. 3 - Mani pul at i ng t he Sel ect ed
Component s Li st for more informat ion.
Throughout t he t abs of t he propert y view, informat ion is displayed in
red, blue, and black. Values displayed in red are est imat ed by UniSim
Design and values displayed in blue are user supplied. Black values
represent calculat ed values or infor mat ion t hat you cannot modify ( i. e.,
Family/ Class on t he I D t ab) .
3. 5. 1 I D Tab
The I D t ab is t he first t ab in t he Hypo propert y view. I f it is t he first t ime
you ar e ent ering a Propert y View, UniSim Design places you on t his t ab.
You can suppl y v al ues di r ect l y f or any of t he component
pr oper t i es, or over w r i t e val ues est i mat ed by Uni Si m Desi gn.
I f y ou change a speci f i ed v al ue, al l pr oper t i es pr ev i ousl y
est i mat ed usi ng t hat speci f i cat i on ar e f or got t en. Cl i ck t he
Est i mat e Unk now n Pr ops but t on t o hav e t he pr oper t i es
r ecal cul at ed.
Fi gur e 3. 16
I f a St ruct ure is
already ent ered,
it is displayed
here. You can
also ent er t he
St ruct ure
direct ly int o t his
cell.
Use t his but t on
t o access t he
UNI FAC
Component
Builder and
supply t he
st ruct ure of
t he Hypo.
3- 23
3. 5. 2 Crit ical Tab
The Crit ical t ab of t he propert y view displays t he base and cr it ical
propert ies. This is t he same informat ion displayed on t he Hypo Group
when t he Base Propert ies radio but t on is select ed.
You can supply or change t he Base Propert ies on t his t ab. The views,
shown in Fi gur e 3. 17, display t he Crit ical t ab before and aft er t he
Est imat e Unknown Props but t on is clicked. Not ice t hat since t he Normal
Boiling Point was less t hat 370 C, only t he Molecular Weight value was
required for t his est imat ion.
3. 5. 3 Point Tab
The Point t ab displays Addit ional Point Propert ies for t he hypot het ical.
There ar e t wo radio but t ons on t he view, which allow you t o t oggle
bet ween t wo t ables of informat ion are t he:
Thermodynamic and Physical Propert ies
Propert y Package Molecular Propert ies
Thermodynamic & Physical Propert ies
This view displays t he Thermodynamic and Physical propert ies for t he
Hypo. UniSim Design est imat es t hese values, based on t he base
Fi gur e 3. 17
t he Minimum
I nformat ion required for
Propert y Est imat ion see
Sect i on 3. 4. 2 -
Suppl y i ng Basi c
I nf or mat i on
3- 24
propert y dat a ent ered and t he select ed est imat ion met hods.
Not ice t hat t he Heat of Comb field is < empt y> . This indicat es t hat
UniSim Design cannot est imat e t his value wit h t he given informat ion.
UniSim Design allows you t o input a value for t his propert y.
The viscosit y coefficient s of A and B are first est imat ed by UniSim
Design based on t he init ial specificat ions from t he Hypo Group view. I f
you want t o calculat e t hese coefficient s, you can override t he
est imat ion by clicking t he Edit Visc Curve but t on. This allows you t o
ent er a set of dat a point s of t emperat ure versus dynamic viscosit y. The
ranges of t emperat ure and viscosit y are - 273. 15 ~ 1500 C and 0~ 10000
cp, respect ively
Fi gur e 3. 18
Fi gur e 3. 19
3- 25
There are t hree but t ons available in t he Edit Viscosit y Cur ve view:
UniSim Design will recalculat e t he values of t he viscosit y coefficient s
based on t he dat a point s you j ust ent ered. The values of t he viscosit y
coefficient s A and B will t hen change from red t o black indicat ing t hat
t hey are calculat ed values.
Propert y Package Molecular Props
This view displays t he Molecular propert ies for t he Hypo. The values
est imat ed are dependent on t he select ed est imat ion met hod for each
propert y.
Some of t he fields in t his view are < empt y> . This indicat es t hat UniSim
Design cannot est imat e t hese values wit h t he informat ion given.
However, you can specify values for t hese propert ies.
But t ons Descr i pt i ons
OK Allows UniSim Design t o accept t he dat a t o perform t he
calculat ions.
Del et e Clears all t he dat a point s in t he dat a t able and closes t he
view aut omat ically.
Cancel Cancels t he operat ion and exit t he view. The dat a point s
you ent ered will not be used in t he calculat ions but t hese
point s will be saved in t he dat a t able wit hout being cleared
so you can make modificat ion lat er.
Fi gur e 3. 20
3- 26
3. 5. 4 TDep Tab
The TDep t ab displays Temperat ure Dependent Propert ies for t he
hypot het ical. There are t hree radio but t ons on t he view, which allow
you t o t oggle bet ween t he t hree different displays of informat ion. The
views available are:
I deal Gas Ent halpy
Vapour Pressure
I deal Gas Gibbs Free Energy of Format ion
I deal Gas Ent halpy
The I deal Gas Ent halpy calculat ion is performed on a Mass Basis. The
reference point for t he equat ion is an ideal gas at 0 K. The unit s for
Mass I deal Gas Ent halpy and Temperat ure are kJ/ kg and degrees
Kelvin, respect ively.
When required, t he I deal Gas Ent halpy equat ion is int egrat ed by UniSim
Design t o calculat e ent halpy. You can select t he different Equat ion
Shape from t he dr opdown list wit hin Equat ion Shape cell. This list
cont ains 4 available Equat ion Shapes t o choose from. The Y Shape and
X Shape for t he equat ions are set on default Shape, and t he Y
Coefficient , Temperat ure coefficient and Temperat ure Shape Norm for
t he equat ions are set t o const ant value 1 here.
Not ice t hat UniSim Design has est imat ed t he Minimum and Maximum
Temperat ur es.
Below t he t emperat ur e range are values for t he I deal Gas Ent halpy
equat ion coefficient s. UniSim Design est imat es t he coefficient s of Poly4
Fi gur e 3. 21
3- 27
equat ion, but you may change any of t he values. And you can also
select any ot her Equat ion Shapes, and set t he value of equat ion
coefficient s.
Vapour Pressure
The Vapour Pressure is calculat ed using t he Modified Ant oine equat ion.
UniSim Design est imat es t he Minimum and Maximum Temperat ure
values based on t he supplied propert ies and est imat ion met hods.
The unit s used for Pressure and Temperat ure are kPa, and degrees
Kelvin, respect ively.
You can select t he different Equat ion Shape from t he drop- down list
wit hin Equat ion Shape cell. The choices for t he Y Shape are available
using t he drop- down list wit hin t he Y Shape cell. For example, if Yvar is
chosen as Y Shape, it means t hat t he Y variables in t he equat ion are
equal t o Y, which repr esent s Vapour Pressure here, and if LogY: log10( y)
is chosen as t he Y Shape, t hen t he Y variables in t he equat ion are
replaced by log10( y) . Similarly, you can select t he Temperat ure Shape
from t he drop- down list wit hin Temp Shape cell. And t he Y Coefficient ,
Temperat ur e coefficient and Temperat ure Shape Norm for t he equat ions
can be set in t heir cell, respect ively.
UniSim Design est imat es t he coefficient s of Ant o5 equat ion, however
you can modify t hese values or choose any ot her Equat ion Shapes.
I deal Gas Gibbs Energy of Format ion
The I deal Gas Gibb' s Energy of Format ion uses Ent halpy as it s propert y
Fi gur e 3. 22
3- 28 Sol i d Hy pot het i cal s
3- 28
t ype and is performed on a Molar Basis. The basis for t he equat ion is
ideal gas at 25 C. UniSim Design est imat es t he Minimum and
Maximum Temperat ure values.
The unit s for Molar Ent halpy and Temperat ure are kJ/ kg mole and
degrees Kelvin, respect ively.
The bot t om sect ion of t he view displays t he values for each of t he Gibbs
Free Energy equat ion coefficient s ( from a t o c) .
UniSim Design est imat es t he Gibbs Free Energy coefficient s if you
supply t he UNI FAC st ruct ure and ent er t he I deal Gas Gibbs Free Ener gy
at 25 C in t he a coefficient cell.
3. 6 Solid Hypot het icals
Solid Hypot het icals can be added t o any Hypo Group, regardless of t he
Group Type. I n t he I ndividual Hypo Cont rols group of t he Hypo Group
view, click t he Add Solid but t on.
When you inst all a solid hypo, you not ice t hat t he Base Propert ies cells
on t he Hypo Group view are displayed as < empt y> .
3. 6. 1 I D Tab
To define t he Solid Hypo, access it s propert y view by highlight ing t he
component name on t he Hypo Group view and clicking t he View but t on.
For hydrat e, you have t o put hydrat e name in t he Chem Formula field in
Fi gur e 3. 23
Solids do not t ake part in
VLE calculat ions, but
t hey do have an effect
on heat balance
calculat ions.
3- 29
Hypo Gr oup view for comput er recognize by following t he rule, which is
summar ize t he number of ever y element in hydrat e and put it behind
t he element t o form a new Chemical formula. Take hydrat es
and for example, you have t o put t heir name in t he Chem
Formula field as and respect ively for comput er
recognize.
The I D t ab of t he Solid Component propert y view is t he same as t hat
for ot her Hypo component s except t hat t he User Props t ab is replaced
by t he PSD t ab and Coal Tab. Not e t hat in t his case, t he Family/ Class is
Alcohol. The Class t ype has no effect on t he values calculat ed for t he
solid component .
3. 6. 2 Props Tab
The Props t ab displays t he basic propert ies of t he component in t wo
groups:
Solid Proper t ies where bulk pr opert ies are ent ered
Coal Analysis where dat a can be ent ered on a possible Coal
Analysis
Solid Propert ies
The minimum informat ion t hat must be supplied includes t he Molecular
Weight and t he Densit y. The appropriat e unit s can also be specified
Fi gur e 3. 24
CaSO
4
H
2
O
CaSO
4
0.5H
2
O
Ca1S1O6H4 Ca1S1O4.5H1
3- 30
wit hin t he cell as shown below.
The ot her Solid Propert ies are described below:
Coal Analysis
As new coal propert y analysis t ool is developed, t his int erface for coal
analysis input is disabled. Please refer t o Sect i on 3.6.6 - Coal Tab for
more informat ion on t he new coal propert y analysis t ool.
3. 6. 3 Point Tab
The only informat ion on t he Point t ab t hat is relevant t o t he Solid is t he
Fi gur e 3. 25
Sol i d Pr oper t y Descr i pt i on
Di amet er Part icle diamet er, if not supplied t his default s t o 1 mm
when t he remaining propert ies are est imat ed.
Spher i ci t y Value bet ween zero and one, wit h one being perfect ly
spherical.
Ar ea/ Uni t
Vol ume
Measure of t he surface area of t he part icle as a
funct ion of t he part icle volume.
3- 31
Heat of Combust ion and Heat of Format ion.
This informat ion is only required if you plan on using a Solid component
as part of a react ion.
3. 6. 4 TDep Tab
Since Solid Hypos do not part icipat e in VLE calculat ions, t heir vapour
pressure informat ion is, by default , set t o zero. However, since solid
component s do affect Heat Balances, t he Specific Heat informat ion can
eit her be est imat ed by UniSim Design, or supplied.
Fi gur e 3. 26
Fi gur e 3. 27
Whi l e ot her Hy pot het i cal s use t he I deal Gas Ent hal py
coef f i ci ent s, sol i ds use t he Speci f i c Heat Capaci t y.
3- 32
3. 6. 5 PSD Tab
The PSD t ab displays t he part icle size dist ribut ion for solids. I t allows
you t o specify PSDs and calculat e various mean and modal diamet ers
for t he ent ered PSD. The PSD t ab is shown below.
Refer t o Sect i on 1. 2. 3 - Mani pul at i ng t he Sel ect ed Component s
Li st and see User Pr op and PSD Tab for mor e informat ion on Part icle
Size Dist ribut ion.
3. 6. 6 Coal Tab
The Coal t ab displays t he coal propert ies for hypo solid component s. I t
allows user t o specify hypo solid component as coal and est imat e it s
Fi gur e 3. 28
3- 33
propert ies. The Coal t ab is shown below.
Refer t o Sect i on 1. 2. 3 - Mani pul at i ng t he Sel ect ed Component s
Li st and see Coal Tab for more informat ion on Coal Pr opert ies.
3. 7 Cloning Library
Component s
You can convert UniSim Design library component s int o Hypot het icals
t hrough t he Clone Library Comps but t on on t he Hypo Group view. When
you click t his but t on, t he Convert Library Comps t o Hypot het ical Comps
view is displayed. Any of t he library component s present in t he current
Fluid Package can be convert ed t o a Hypot het ical.
This view is made up of t wo sect ions, t he Source Component s group
Fi gur e 3. 29
Fi gur e 3. 30
By using t he Add New
Hypo Group but t on, you
do not have t o ret urn t o
t he Simulat ion Basis
Manager t o creat e a
Hypo Group.
3- 34 Hy po Cont r ol s
3- 34
and t he Hypo Groups.
3. 7. 1 Convert ing a Library
Component t o a Hypo
When convert ing a library component t o a Hypo, follow t he procedure
out lined below. Fi gur e 3. 30 is used as a reference.
1. Select t he Component Li st which cont ains t he t arget library
component . I n t his case, Component Li st - 1 is t he select ed
component list .
2. From t he Available Library Comps group, select t he component t o
clone. I n t his case, 1- Pr opanol is select ed.
3. Select t he t arget Hy po Gr oup, where t he new Hypo is t o be placed.
Hy poAl cohol is select ed.
4. Decide if you want t o replace all inst ances of t he source component
( 1- Propanol) wit h t he new Hypo. Act ivat e t he Repl ace Al l
I nst ances checkbox t o do t his. I n Fi gur e 3. 30 t he checkbox is
act ivat ed.
5. To complet e t he conversion, click t he Conv er t t o Hy po( s) but t on.
6. The new Hypo appears in t he Hypo Component s group, and has an
ast erisk ( 1- Pr opanol * ) aft er it s name, signifying t hat it is a
hypot het ical.
7. Close t he view t o r et urn t o t he Hypo Group view.
3. 8 Hypo Cont rols
The manipulat ion commands for hypot het icals are cont ained on t he
Hypot het icals t ab of t he Simulat ion Basis Manager. The Hypo Cont rols
are t he but t ons cont ained wit hin t he Hypot het ical Quick Reference
Component Li st s Allows you t o select t he component list t hat cont ains t he
library component you want t o clone.
Av ai l abl e Li br ar y
Comps
Select s t he component you want t o convert int o a
hypot het ical.
Repl ace ALL
I nst ances
I f you want t o replace t he library component wit h t he Hypo
in every Fluid Package t hat cont ains t he library component ,
act ivat e t his checkbox. I f you only want t o replace t he
library component s in t he highlight ed Fluid Package, do not
act ivat e t he checkbox.
Hy po Gr oup Select s t he Hypot het ical Group in which you want t he
convert ed library component placed.
Hy po
Component s
Displays all t he hypot het ical component s present in t he
select ed hypot het ical group. When a library component is
convert ed int o a hypot het ical, it is list ed here.
3- 35
group as shown below:
3. 8. 1 Viewing Groups
Not ice t hat t he Hypot het ical Quick Reference group displays t he names
of hypot het ical groups and component s. The component s are list ed in
t he Hypo Name column and t he group t o which each component
belongs is list ed in t he Group Name column.
From t he Group Name column, select t he Group t hat you want t o view,
and click t he View Group but t on. UniSim Design displays t he Hypo
Group view for t hat Hypo Group. All t he Hypo component s t hat are part
of t he group appear on t his view.
3. 8. 2 Moving Hypos
When hypot het ical component s are creat ed in UniSim Design, t hey are
creat ed wit hin a Hypo Group, and become par t of t he group. Aft er
adding a hypot het ical component t o a cer t ain group, you may want t o
move it t o anot her exist ing group. You can accomplish t his t hrough t he
Hypo Cont rols. From t he Hypot het ical Quick Reference group, click t he
Move Hypo but t on. This produces t he following view:
Fi gur e 3. 31
Fi gur e 3. 32
By clicking t he Add New
Hypo Group but t on,
UniSim Design allows you
t o add a new Hypo Group
while t his view has focus.
3- 36 Ref er ences
3- 36
Follow t his procedure t o move a Hypo t o a different Hypo Group:
1. From t he Hypo Component s group, select t he Hypo t hat you want t o
move.
2. Select t he Target Hypo Group t o which t he Hypo is being moved.
3. Click t he Sw i t ch t o Gr oup but t on, which becomes available when a
select ion is made in bot h t he Hypo Component s group and Target
Hypo Group.
4. When you are finished moving groups, close t he view and ret urn t o
t he Hypot het icals t ab of t he Simulat ion Basis Manager.
3. 9 References
1
Reid, R.C., Prausnit z, J. M., Poling, B.E., The Propert ies of Gases & Liquids, 4t h
edit ion, McGraw- Hill, 1987.
Uni Si m Desi gn Oi l Manager 4- 1
4- 1
4 UniSim Design Oil
Manager
4.1 I nt r oduct i on ............. ........................................................... .......... 3
4.2 Oi l Char act er i zat i on .. ........................................................... .......... 4
4.2.1 Laborat ory Dat a. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
4.2.2 Convent ional Dist illat ion Dat a . .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
4.2.3 Dat a Report ing Basis . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 6
4.2.4 Physical Propert y Assay Dat a .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 6
4.2.5 Propert y Curve Basis . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
4.2.6 Common Laborat ory Dat a Correct ions.. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
4.2.7 Default Correlat ions .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
4.3 Pet r ol eum Fl ui ds Char act er i zat i on Pr ocedur e ...................... .......... 8
4.3.1 I nit ializat ion . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
4.3.2 St ep One - Charact erize Assay .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 9
4.3.3 St ep Two - Generat e Hypocomponent s. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 10
4.3.4 St ep Three - I nst all Oil ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 10
4.3.5 User Propert y . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 10
4.3.6 Correlat ions . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 10
4.4 Oi l Char act er i zat i on Vi ew .................................................... .........11
4.5 Char act er i zi ng Assays.......................................................... .........14
4.5.1 I nput Dat a Tab .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 16
4.5.2 Calculat ion Default s Tab .. .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 40
4.5.3 Working Curves Tab. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 42
4.5.4 Plot s Tab. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 43
4.5.5 Correlat ions Tab. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 44
4.5.6 User Curves Tab. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 46
4.5.7 Not es Tab .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 47
4- 2 Uni Si m Desi gn Oi l Manager
4- 2
4.6 Hy pocomponent Gener at i on ................................................ .........47
4.6.1 Dat a Tab . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 48
4.6.2 Correlat ions Tab. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 54
4.6.3 Tables Tab.. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 55
4.6.4 Propert y Plot Tab . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 56
4.6.5 Dist ribut ion Plot Tab .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 57
4.6.6 Composit e Plot Tab.. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 59
4.6.7 Plot Summary Tab... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 60
4.6.8 Not es Tab .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 60
4.7 User Pr oper t y ........... ........................................................... .........61
4.7.1 User Propert y Tab ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 61
4.7.2 User Propert y View.. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 62
4.8 Cor r el at i ons & I nst al l at i on ................................................... .........64
4.8.1 Correlat ion Tab .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 64
4.8.2 Correlat ion Set View.. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 66
4.8.3 I nst all Oil Tab . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 69
4.9 TBP Assay - Ex ampl e ........................................................... .........71
4.9.1 I nit ializat ion . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 72
4.9.2 St ep 1 - I nput Assay Dat a . ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 73
4.9.3 St ep 2 - Cut Assay int o Hypocomponent s .. .. ... .. ... .. .. ... .. ... .. .. ... .. .. 79
4.9.4 St ep 3 - Transfer I nformat ion t o Flowsheet .. ... .. ... .. .. ... .. ... .. .. ... .. .. 82
4.9.5 Fluid Package Associat ion .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 83
4.10 Sul f ur Cur ve - Ex ampl e ...................................................... .........84
4.10. 1 Fluid Package .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 84
4.10. 2 I nst all a User Propert y .. .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 85
4.10. 3 I nst all t he Assay ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 86
4.10. 4 Creat e t he Blend ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 88
4.10. 5 Result s . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 88
4.11 Ref er ences.............. ........................................................... .........90
4- 3
The Oil Charact erizat ion environment can be accessed from t he Oil
Manager t ab of t he Simulat ion Basis manager or by clicking t he Oil
Environment icon on t he t oolbar. To ent er t he Oil Charact erizat ion
environment , at least one fluid package must exist in t he case.
Hypot het ical ( pseudo) component s must be compat ible wit h t he
propert y met hod being used by t he fluid package.
All hypocomponent s t hat are defined wit hin t he Oil Charact erizat ion
environment are assigned t o a Hypo group and inst alled in an
associat ed fluid package. Since Light End calculat ions for an oil require
informat ion from t he propert y met hod being used by t he associat ed
fluid package, t he hypocomponent cannot be shared among different
fluid packages as regular hypot het ical component s can. However, you
can st ill use t he same hypocomponent in t he non- associat ed fluid
packages by adding t hem as hypot het icals, via t he Add Hypo or Add
Group but t on on t he Select ed t ab of t he Component List propert y view.
The Oil Charact erizat ion environment provides a locat ion where t he
charact erist ics of a pet roleum fluid can be represent ed by using
discret e hypot het ical component s. Physical, crit ical, t hermodynamic
and t ransport propert ies are det ermined for each hypot het ical
component using correlat ions t hat you select . The fully defined
hypocomponent can t hen be inst alled in a st ream and used in any
flowsheet .
UniSim Design defines t he hypocomponent by using assay dat a which
you provide. The feat ures available for t he input of assay dat a minimize
t he t ime requir ed for dat a ent r y. For inst ance, defined assays can be
cloned, import ed and export ed. Export ed assays can be used in ot her
fluid packages or in ot her cases alt oget her.
Some of t he feat ur es exclusive t o t he oil environment include:
Providing laborat ory assay dat a
Cut t ing a single assay
Blending mult iple assays
Assigning a user propert y t o hypocomponent s
Select ing correlat ion set s t o det ermine propert ies
I nst alling hypocomponent int o a st ream
Viewing t ables and plot s for your input and for t he charact erized
fluid
Oil Environment I con
Hy pot het i cal s for
hypo cont rols.
4- 4 Oi l Char act er i zat i on
4- 4
4. 2 Oil Charact erizat ion
The pet r oleum charact erizat ion met hod in UniSim Design convert s your
laborat ory assay analyses of condensat es, crude oils, pet r oleum cut s,
and coal- t ar liquids int o a series of discret e hypot het ical component s.
These pet roleum hypocomponent s provide t he basis for t he propert y
package t o predict t he remaining t hermodynamic and t ransport
propert ies necessary for fluid modeling.
UniSim Design produces a complet e set of physical and crit ical
propert ies for t he pet r oleum hypocomponent wit h a minimal amount of
informat ion. However, t he more informat ion you can supply about t he
fluid, t he more accurat e t hese propert ies are, and t he bet t er UniSim
Design predict s t he fluid' s act ual behaviour.
4. 2. 1 Laborat ory Dat a
Accurat e volat ilit y charact erist ics are vit al when represent ing a
pet roleum fluid in your process simulat ion. UniSim Design accept s five
st andard laborat ory analyt ical assay procedures:
True boiling point dist illat ion ( TBP)
ASTM D86 and ASTM D1160 dist illat ions ( Separat ely or
Combined)
ASTM D2887 simulat ed dist illat ion
Equilibrium flash vapourizat ion ( EFV)
Chromat ographic analysis
The charact erizat ion procedure performs it s calculat ions based on an
int ernally calculat ed TBP curve. I f you supply an ASTM or EFV
dist illat ion curve, it is convert ed t o a TBP curve using st andard met hods
described in t he API Dat a Book. I f you do not supply any dist illat ion
dat a, t hen an average TBP dist illat ion curve is generat ed for you based
on t he overall molecular weight , densit y, and Wat son ( UOP) K fact or of
your fluid.
4. 2. 2 Convent ional Dist illat ion
Dat a
The five primary t ypes of assay dat a accept ed by t he Pet roleum
Charact erizat ion Procedur e in UniSim Design are list ed here and
explained in t he following sect ions.
True Boiling Point analysis
ASTM D86 and 1186 Dist illat ions
The Wat son ( UOP) K
fact or is an approximat e
index of paraffinicit y, wit h
high values corresponding
t o high degrees of
sat urat ion:
where t he mean average
boiling point is in degrees
Rankine.
K
Mean Avg. BP ( )
1
3
--
sp gr 60F / 60F
------------------------------- =
4- 5
ASTM D2887
Equilibrium Flash Vaporizat ion
Chromat rographic analysis
True Boiling Point ( TBP) Analysis
A TBP analysis is performed using a mult i- st age bat ch fract ionat ion
apparat us operat ed at relat ively high reflux rat ios ( 15 - 100 t heoret ical
st ages wit h reflux rat ios of 5 t o 1 or great er) . TBP dist illat ions
conduct ed at eit her at mospheric or vacuum condit ions are accept ed by
t he charact erizat ion procedure.
The pet roleum fluid' s bubble point is a mult i- component equilibrium
condit ion such t hat t here is an incipient vapour phase forming. This
would, in effect , be a single- st age of fract ionat ion as opposed t o t he
highly refluxed operat ion of a TBP analysis.
ASTM D86 and D1160 Dist illat ions
ASTM D86 and ASTM D1160 dist illat ions also employ bat ch
fract ionat ion apparat us, but t hey are conduct ed using non- refluxed
Engler flasks. Two st andard ASTM dist illat ions are support ed: ASTM
D86, used for light t o medium pet roleum fluids, and ASTM D1160,
carried out at varying vacuum condit ions and used for heavier
pet roleum fluids. For ASTM D86 dist illat ion, UniSim Design can correct
for baromet ric pressure or cracking effect s.
ASTM D2887
ASTM D2887 is a simulat ed dist illat ion curve generat ed from
chromat ographic dat a. The result ing boiling point curve is report ed on a
weight percent basis.
Equilibrium Flash Vaporizat ion
An EFV curve is generat ed by a series of experiment s conduct ed at
const ant pressure ( 1 at m) . The result s relat e t he t emperat ure versus
volume percent of liquid dist illed, where t he t ot al vapour is in
equilibrium wit h t he unvaporized liquid.
The init ial boiling point
( I BP) of a TBP curve
does not correspond t o
t he bubble point
t emperat ure of t he
pet roleum fluid at
at mospheric pressure.
4- 6 Oi l Char act er i zat i on
4- 6
Chromat ographic Analysis
A Chromat ographic analysis is a simulat ed dist illat ion performed by
passing a small amount of t ot ally vaporized sample t hrough a packed
gas chromat ograph column. The relat ive amount s of t he sample t hat
appear in each st andard " chromat ographic" hydrocarbon group
( paraffinic, aromat ic and napht haline gr oups, ranging from C6 t o C30)
are t hen det ect ed and report ed.
4. 2. 3 Dat a Report ing Basis
All of t he dist illat ion analyzes described above are report ed using one of
t he following fract ional bases ( assay basis) :
Liquid volume percent or liquid volume fract ions
Mole percent or mole fract ions
Mass percent or mass fract ions
UniSim Design accept s TBP and Chromat ographic analyzes in any one
of t he t hree st andard bases. However, due t o t he form of t he API Dat a
Book conversion curves, EFV, ASTM D86 and ASTM D1160 dist illat ions
must be supplied on a liquid volume basis, and ASTM D2887 are only
report ed on a weight basis.
4. 2. 4 Physical Propert y Assay
Dat a
As you supply more informat ion t o UniSim Design, t he accuracy of t he
Pet roleum Charact erizat ion increases. Supplying any or all of bulk
molecular weight , bulk densit y or bulk Wat son ( UOP) K fact or increases
t he accuracy of your hypocomponent propert ies. Appropriat ely, if you
supply laborat ory curves for molecular weight , densit y and/ or viscosit y,
t he accuracy increases furt her.
I f you cannot supply propert y curve dat a, UniSim Design generat es
int ernal curves using t he available informat ion. This informat ion is
applied using correlat ions. You can change t he default set of propert y
correlat ions as required.
Refer t o Appendi x B -
Oi l Met hods &
Cor r el at i ons for
correlat ions used in t he
Oil Environment .
4- 7
4. 2. 5 Propert y Curve Basis
Physical proper t y analyzes are normally report ed by a laborat ory using
one of t he following t wo convent ions:
An I ndependent assay basis where t he propert y assay volume
fract ions do not correspond on a one- t o- one basis wit h t he
dist illat ion assay fract ions.
A Dependent assay basis, where a common set of assay
fract ions are ut ilized for bot h t he dist illat ion curve and t he
physical pr opert y curves.
Physical proper t ies are average values for t he given range, and hence
are midpoint values. Dist illat ion dat a report s t he t emperat ure when t he
last drop of liquid boils off for a given assay range; t herefore dist illat ion
is an endpoint propert y. Since all dependent input propert y curves are
report ed on t he same endpoint basis as t he dist illat ion cur ve, t hey are
convert ed by UniSim Design t o a midpoint basis. I ndependent pr opert y
curves are not alt ered in any manner befor e being used in t he
charact erizat ion, since t hey are already defined on a midpoint basis.
4. 2. 6 Common Laborat ory Dat a
Correct ions
Wit h ASTM D86 dat a, correct ion procedures are available t o modify t he
laborat ory result s for bot h baromet ric pressure and t hermal cracking
effect s, which result in t he degradat ion of t he sample at high dist illat ion
t emperat ures. These correct ions ar e somet imes performed by t he
laborat ory. I f t he correct ions have not already been applied, t he
Charact erizat ion procedure has opt ions available t o apply t he necessary
correct ions before commencing calculat ions.
4. 2. 7 Default Correlat ions
When you begin a pet roleum charact erizat ion session, UniSim Design
already has a set of default correlat ions for generat ing physical and
crit ical propert ies of t he hypocomponent . You may change any of t he
correlat ions at any t ime.
Refer t o Sect i on 4. 8.2 - Cor r el at i on Set Vi ew for a list ing of
available correlat ions or Appendi x B - Oi l Met hods & Cor r el at i ons
for a descript ion of each correlat ion.
4- 8 Pet r ol eum Fl ui ds Char act er i zat i on
4- 8
4. 3 Pet roleum Fluids
Charact erizat ion
Procedure
4. 3. 1 I nit ializat ion
Before ent ering t he Oil Charact erizat ion environment , you are required
t o creat e a fluid package wit h a specified Propert y Package at t he very
minimum. The Associat ed Propert y Package must be able t o handle
hypot het ical component s ( i. e., a St eam Package is not allowed) .
I f you want t o use library component s t o represent t he Light Ends
port ion of your assay, it is best t o select t he component s prior t o
ent ering t he Oil Charact erizat ion environment ( if you forget t o do t his,
you can ret urn lat er t o t he Component s t ab and select t he
component s) .
The Oi l Manager t ab of t he Basis Manager view is shown below:
The Associat ed Fluid Package for t he Oil serves t wo primary funct ions:
Provides t he light end component s.
I dent ifies t o which Fluid Package t he Hypo group ( oil) is being
inst alled.
The fluid package t hat is used in t he Oil Charact erizat ion environment
can be select ed from t he Associat ed Fluid Package drop- down list . To
ent er t he Oil environment , select t he Ent er Oil Environment but t on as
shown in Fi gur e 4. 1, or select t he Oil Environment but t on from t he
Fi gur e 4. 1
4- 9
t oolbar. The following figure illust rat es t he makeup of a t ypical oil:
An Oil or Blend is comprised of any number of Assays. Each individual
Assay cont ains specific informat ion wit h respect t o t he Bulk Propert ies,
Boiling Point Curve and Propert y Curves. For t he Bulk Propert ies, you
may supply Molecular Weight , Mass Densit y, Wat son ( UOP) K fact or,
and/ or Viscosit y. You can provide t he Boiling Point curve in any one of
t he format s displayed in t he Fi gur e 4. 2. During calculat ions, UniSim
Design aut omat ically convert s all curves t o a TBP basis. You also have
t he opt ion of supplying Molecular Weight , Mass Densit y, and/ or
Viscosit y curves.
There ar e t hree general st eps you must follow when creat ing an oil:
1. charact erize assay
2. generat e hypocomponent
3. inst all oil in flowsheet .
4. 3. 2 St ep One - Charact erize
Assay
Ent er t he pet roleum assay dat a int o UniSim Design via t he Assay t ab of
t he Oil Charact erizat ion view. UniSim Design uses t he supplied Assay
dat a t o generat e int ernal TBP, molecular weight , densit y and viscosit y
curves, referred t o as Working Curves. See Sect i on 4.5 -
Char act er i zi ng Assay s for more det ails.
Fi gur e 4. 2
OI L
( blend)
Assay 1
Assay 3
Bulk
Propert ies
Boiling Point
Curve
Propert y Curves
Dependent /
I ndependent
Molecular Weight
Mass Densit y
Wat son ( UOP) K
Viscosit y
TBP
ASTM D86
ASTM D1160
ASTM D86- D1160
ASTM D2887
EFV
Chromat ograph
Molecular Weight
Mass Densit y
Viscosit y
Assay 2
I t is a good idea t o open
t he Trace Window before
you st art t he
charact erizat ion, since it
displays import ant
informat ion during Oil
Charact erizat ion
calculat ions.
4- 10 Pet r ol eum Fl ui ds Char act er i zat i on
4- 10
4. 3. 3 St ep Two - Generat e
Hypocomponent s
Hypocomponent s are generat ed from t he Working Curves via t he Cut /
Blend t ab of t he Oil Charact erizat ion view. This pr ocess is explained in
Appendi x B - Oi l Met hods & Cor r el at i ons. See Sect i on 4.6 -
Hy pocomponent Gener at i on for t he procedure.
4. 3. 4 St ep Three - I nst all Oil
Once t he Blend is charact erized sat isfact orily, inst all hypocomponent
int o your UniSim Design case via t he I nst all Oil t ab of t he Oil
Charact erizat ion view. You can inst all t he oil as a defined st ream by
providing a St ream name. The hypocomponent is also added t o a
dist inct Hypo group and t o t he associat ed fluid package. See Sect i on
4. 8. 3 - I nst al l Oi l Tab for more det ails.
4. 3. 5 User Propert y
I n addit ion t o t he t hree basic st eps required t o charact erize an oil in
UniSim Design, user propert ies can be added, modified, delet ed, or
cloned. User Pr opert ies can be creat ed from t he Oil Manger or in t he
Basis Environment . A user pr opert y is any propert y t hat can be
calculat ed on t he basis of composit ion. Refer t o Sect i on 4.7 - User
Pr oper t y for more informat ion.
4. 3. 6 Correlat ions
Correlat ions can be select ed via t he Correlat ion t ab of t he Oil
Charact erizat ion view. UniSim Design allows you t o select from a wide
variet y of correlat ions used in bot h t he det erminat ion of working curves
and in t he generat ion of hypocomponent . See Sect i on 4. 8.1 -
Cor r el at i on Tab.
Al l of t he i nf or mat i on used i n gener at i ng your
hy pocomponent i s st or ed w i t h t he case. Thi s i ncl udes:
Assay s and t hei r associ at ed Opt i ons, Pr oper t y Cur ves and
Bul k Pr oper t i es, User Pr oper t i es, t he Cor r el at i ons used f or
gener at i ng t he pseudo- component s, t he Const i t uent oi l s
( w i t h f l ow r at es) f or bl ends, and t he f l ow sheet st r eam i n
w hi ch each oi l w as i nst al l ed. Thi s i nf or mat i on i s av ai l abl e t he
nex t t i me you open t he case.
4- 11
4. 4 Oil Charact erizat ion View
When you ent er t he Oil Charact erizat ion environment , t he following
view appears:
This view is t he Oil Charact erizat ion envir onment . There ar e five t abs
which represent t he main areas of t he environment and are described
below:
The Clear All, Calculat e All, and Oil Out put Set t ings. . . but t ons are
available on any t ab of t he Oil Charact erizat ion pr opert y view.
I f you select t he Cal cul at e Al l but t on, UniSim Design calculat es
all Assays and Blends. This opt ion is useful if you have several
Assays and/ or Blends and you want t o see t he global effect of a
change in t he correlat ion.
Fi gur e 4. 3
Tab Descr i pt i on
Assay Add, edit , delet e, clone, import or export Assays ( see
Sect i on 4. 5 - Char act er i zi ng Assay s) .
Cut / Bl end Add, edit , delet e or clone Blends ( see Sect i on 4.6 -
Hy pocomponent Gener at i on) .
User
Pr oper t y
Add, edit , delet e or clone User Propert ies ( see Sect i on 4. 7
- User Pr oper t y) .
Cor r el at i on Add, edit , delet e or clone Correlat ion Set s ( see Sect ion
Sect i on 4. 8.1 - Cor r el at i on Tab) .
I nst al l Oi l I nst all hypocomponent int o a st ream in a UniSim Design
case ( see Sect i on 4. 8.3 - I nst al l Oi l Tab) .
4- 12 Oi l Char act er i zat i on Vi ew
4- 12
I f you select t he Cl ear Al l but t on, UniSim Design displays t he
following warning:
I f you want t o delet e all Oil Charact erizat ion informat ion select
Yes.
Select ing t he Oi l Out put Set t i ngs. . . but t on result s in t he Oil
Out put Set t ings propert y view.
Oil Out put Set t ings View
On t his view, you can set t he init ial boiling point ( I BP) and final boiling
point ( FBP) cut point s on a liquid volume, mole or mass percent age
basis. These values are used t o det ermine t he init ial and final boiling
t emperat ures of t he TBP working curve. The default values are 1% for
t he I BP and 98% for t he FBP.
I f for example, an I BP value of 1% is specified, t he init ial boiling point
becomes t he weight ed average boiling t emperat ure of all component s
t hat boil off in t he first volume percent . The final boiling point is
det ermined in a similar manner. I f 98% is used for t he FBP, t he final
boiling t emperat ure becomes t he weight ed average boiling t emperat ure
of all t he component s t hat boil off in t he last 2 volume percent . The
ends of t he curve are ' st ret ched' t o fill t he assay range of 0 t o 100%.
On t he Oil Out put Set t ings view, you can select t he default ASTM D86
I nt erconversion Met hod TBP conversion t ype from t he Default D86
Curve Type dr opdown list :
API 1974
1

API 1987
2

Fi gur e 4. 4
Fi gur e 4. 5
Oil I nput set t ings are
accessed t hrough t he
Preferences view.
4- 13
API 1994
3

Edmist er- Okamot o 1959
4

You can also select t he ASTM D2887 I nt erconversion met hod from t he
following:
API 1987
5
API 1994 I ndirect
6
API 1994 Direct
7
The Oil Out put Set t ings are saved along wit h your simulat ion case.
They can be accessed eit her wit hin t he Oil manager or t hrough t he
Simulat ion menu bar opt ion in t he Main Simulat ion environment .
Changing t he I BP and FBP in t he Oil Out put Set t ings will affect t he
following calculat ions:
Blend Pr opert ies Table and Plot s
Boiling Point Ut ilit y
Cold Propert ies Ut ilit y
Column specs ( Cut Point , Gap Cut Point , Flash Point , RON Point )
Column Profiles
When I BP and FBP changes ar e made, all necessary calculat ions are
aut omat ically performed.
The ASTM D86 and ASTM D2887 i nt er conv er si on met hods do
not af f ect col umn speci f i cat i ons, si nce each r el at ed
col umnspec has i t s ow n i ndependent set t i ng. I f y ou w ant t o
change t he col umn speci f i cat i ons, cl i ck t he Change
I nt er conver si on Met hods f or Ex i st i ng Col umn Specs but t on.
Uni Si m Desi gn ask s you t o conf i r m t hat you w ant t o gl obal l y
i mpose t hese changes.
4- 14 Char act er i zi ng Assay s
4- 14
4. 5 Charact erizing Assays
The Assay t ab of t he Oil Charact erizat ion view is shown below:
The Available Assays ar e list ed in t he left port ion of t he view. The
following Assay manipulat ion but t ons are available:
For a highlight ed Assay, you can edit t he name in t he Name field and
provide a descript ion in t he Descript ion t ext box found in Assay
I nformat ion group.
To creat e a new assay or edit an exist ing assay you can click t he Add or
View but t ons, respect ively. This opens t he Assay propert y view for t he
new or exist ing assay.
When t he Oil I nput Preferences but t on under t he Assay I nformat ion
group is clicked, t he Session Preferences view opens t o t he Oil I nput
Fi gur e 4. 6
C
Vi ew Edit t he current ly highlight ed Assay
Add Creat e a new Assay
Del et e Erase t he current ly highlight ed Assay
Cl one Creat e a new Assay wit h t he same propert ies as t he
current ly highlight ed Assay. UniSim Design immediat ely
opens a new Assay view
I mpor t Bring a saved assay int o t he current case
Ex por t Save an assay t o disk so t hat it can be used in ot her cases
TBP Assay - Ex ampl e
for charact erizing
assays.
UniSim Design does not
prompt for confirmat ion
when delet ing an assay,
so be careful when you
are using t his command.
However, UniSim Design
does not delet e an assay
t hat is being used by a
blend.
I mport ed and Export ed
assays have a filename
form * . oil.
4- 15
t ab. From her e you can set t he input default s for your case.
When a new case is creat ed, t he met hods specified in t he Oil I nput
set t ings init ialize t he Oil Out put set t ings. However, any changes made
aft erwards t o eit her set t ings group are independent .
Assay Propert y View
The Assay proper t y view is shown below:
The Assay proper t y view consist s of seven t abs, which are described
Fi gur e 4. 7
Fi gur e 4. 8
The appearance of t he
Assay propert y view
depends on how you
define t he assay in t he
Assay Definit ion group
and which radio but t on
is select ed in t he I nput
Dat a group.
4- 16
below:
There are four obj ect s found at t he bot t om of t he propert y view and ar e
described below:
The following sect ions out line each of t he t abs cont ained wit hin t he
Assay view ( accessed via t he View or Add but t on) .
4. 5. 1 I nput Dat a Tab
The minimum amount of informat ion t hat UniSim Design requires t o
charact erize a pet roleum fluid is eit her:
a laborat ory dist illat ion curve, or
t w o of t he following t hree bulk propert ies: Molecular Weight ,
Densit y, or Wat son ( UOP) K fact or.
However, any addit ional informat ion such as dist illat ion cur ves, bulk
propert ies and/ or propert y curves, should be ent ered if possible. Wit h
more supplied informat ion, UniSim Design produces a more accurat e
Tab Descr i pt i on
I nput Dat a Allows you t o define and specify t he Assay.
Cal cul at i on
Def aul t s
Allows you t o set t he calculat ion met hods and
ext rapolat ion met hods for t he assay and assay
propert y curves.
Wor k i ng Cur v es Displays a t able of Assay Working curves.
Pl ot s Allows you t o view any of t he input assay curves in
graphical form.
Cor r el at i ons Allows you t o edit t he individual propert y conversion
met hods used.
User Cur ves Allows you t o at t ach available user propert ies t o t he
assay.
Not es Allows you t o at t ach relevant comment s t o t he assay.
Name You can provide t he name of t he Assay in t he Name cell
( maximum 12 charact ers) .
Assay St at us The st at us bar is displayed at t he bot t om of t he screen:
Assay Was Not Cal cul at ed. You have not provided
enough Assay informat ion t o det ermine a solut ion ( or
you have enough informat ion and have not clicked t he
Calculat e but t on) .
Assay Was Cal cul at ed. You have provided Assay
informat ion, clicked t he Calculat e but t on, and
obt ained a solut ion.
An Er r or Was Found Dur i ng Cal cul at i on. The Trace
Window usually shows a descript ion of t he t ype of
Error.
Cal cul at e Click t his but t on t o calculat e t he Assay.
Del et e Click t his but t ons t o delet e t he current Assay.
There is no confirmat ion
when you delet e an
assay, unless it is being
used by a blend, in
which case you cannot
delet e it .
high values corresponding
t o high degrees of
sat urat ion:
where t he mean average
boiling point is in degrees
Rankine.
K
Mean Avg. BP
3
sp gr 60F / 60F
----------------------------- =
4- 17
final charact erizat ion of your oil.
The I nput Dat a t ab is shown below:
The I nput Dat a t ab is split int o t wo groups: t he Assay Definit ion and
I nput Dat a groups. The Assay Definit ion group is where t he assay t ype
and use of propert y curve, light ends dat a and bulk propert ies are
defined. The I nput Dat a group is where t he dist illat ion, propert y curve,
light ends and propert y dat a is act ually input t ed.
When y ou open t he Assay vi ew t o t he I nput Dat a t ab, al l t hat
i s di spl ay ed i s t he Assay Dat a Type and Bul k Pr oper t i es dr op-
dow ns. New i nput f i el ds ar e added as y ou speci f y t he
i nf or mat i on f or your oi l .
Fi gur e 4. 9
For each of t he t hr ee pr oper t y cur v es, Mol ecul ar Wei ght ,
Densi t y and Vi scosi t y , y ou hav e t he f ol l ow i ng opt i ons: Not
Used, Dependent , or I ndependent . I f y ou sw i t ch t he st at us
t o Not Used af t er y ou have ent er ed assay dat a, al l y our dat a
f or t hat pr oper t y cur ve i s l ost w hen y ou r et ur n y our sel ect i on
t o Dependent or I ndependent .
Specify which
individual I nput
Dat a curves are t o
be included.
Depending on t he specificat ions made in t he
Assay Definit ion group. These radio but t ons
become visible. Each radio but t on makes a
different ent ry field visible.
The layout of I nput Dat a
group depends largely on
t he set t ings you choose in
t his group.
Opt ions relat ed t o
t he Assay Dat a
Type are
displayed in t his
area.
The ent ry fields displayed in t his t able depend on which
radio but t on is select ed.
4- 18
Light Ends Handling & Bulk Fit t ing
I f you have a light - ends analysis along wit h light - ends free input curves
and t ot al bulk propert ies or light - ends free bulk propert ies you can use
t he UniSim Design oil manager t o combine t he light - ends analysis wit h
t he light - ends free input curves t o mat ch t he specified bulk propert ies.
This funct ionalit y is clearly seen in t he case of chromat ographic input ,
where you may want t o input t he light - ends along wit h t he C6+ as t he
chromat ographic dat a groups. Because of t he nat ure of t he analysis,
t he chromat ographic dat a is light - ends free.
Light Ends Analysis Versus Calculat ed TBP Curve
I deally, for t he light - ends free dist illat ion input curve, t he TBP at 0%
should coincide wit h t he highest NBP in t he light - ends component s wit h
non- zero composit ions, see Case B in Fi gur e 4.10. However, due t o
imperfect input dat a or ext rapolat ion, t he calculat ed TBP at 0% may be
lower t han t he t op NBP for light ends ( Case A in Fi gur e 4.10) or higher
t han t he t op NBP for light ends ( Case C in Fi gur e 4. 10) . To avoid
overlapping or discont inuit y, t hese t wo cases must be properly handled.
I n Case A, t he highest t emperat ure of t he non- zero component in light
ends is above t he TBP at 0%. I n t his case, we need t o eliminat e t he
point s having TBP lower t han t he t op light - ends t emperat ure. Aft er t he
eliminat ion, t he remaining port ion of t he light - ends free TBP curve are
re- scaled t o 100%, and t hen a new set of st andard 51 point s calculat ion
t ables are regenerat ed from t he remaining port ion of t he corresponding
Fi gur e 4. 10
4- 19
curves.
I n Case C, t he t op light - ends t emperat ure is below t he TBP at 0%.
Since t he ext rapolat ion may not be accurat e, more t rust is put on t he
light - ends analysis and hence assign t he t op light - ends t emperat ure as
t he TBP at 0%. To avoid a sudden j ump in t he dist illat ion curve, t he
first 20% of t he dist illat ion curve is also smoot hed.
Curve Part it ion for Bulk Propert y Fit t ing
To allow piecewise fit t ing for a bulk pr opert y, a propert y curve is
divided int o t hree sect ions: head, main, and t ail. The ending % of t he
head sect ion and beginning % of t he t ail sect ion can be specified. Each
sect ion can have an independent adj ust ing weight fact or as shown in
t he figure below.
For piecewise bulk propert y fit t ing t here are t wo concerns t o be
addressed. First , since each sect ion can have an independent adj ust ing
weight fact or, t here may be a discont inuit y at t he boundary of t he t wo
sect ions. Second, how t o ensure relat ively fast convergence wit h
uneven adj ust ment of t he propert y concerned. For t he first concern,
discont inuit y is avoided by using linear int erpolat ion bet ween t wo
sect ions. For t he second concern, t he weight fact or is normalized first
and t hen t he following equat ion is used t o calculat e t he new point
propert y value from t he old point propert y value:
where:
New[ i] = t he new propert y value at point i
Wt [ i] = t he normalized weight fact or at point i
Rat io = t he calculat ed uniform adj ust ing rat io
Fi gur e 4. 11
( 4. 1) New i | | 1 Wt i | | Ratio 1 ( ) + | | Old i | | =
4- 20
Old[ i] = t he old propert y value at point i
UniSim Design allows you t o specify if a given curve cont ains light - ends
cont ribut ions, set if a specified bulk propert y cont ains light - ends and
part it ion a propert y curve so t hat some sect ions can be adj ust ed more
t han ot hers.
The Light Ends Handling & Bulk Fit t ing Opt ions view is accessed by
clicking t he Light Ends Handling & Bulk Fit t ing Opt ions but t on.
The light ends handling and bulk fit t ing opt ions are described below:
The last five columns are used for piecewise bulk propert y fit t ing.
When fit t ing a given bulk propert y value t he int ernal calculat ion curve,
eit her based on t he input curve or calculat ed from a correlat ion, is
divided int o t hree sect ions. Each of t he t hree sect ions can be
independent ly adj ust ed.
Fi gur e 4. 12
Col umn Descr i pt i on
I nput Cur ve Displays all t he possible input curves, including user
propert y curves.
Cur v e I ncl L.E. Specifies if t he corresponding input curve includes light
ends. I f an input curve is not used, t he corresponding
checkboxes are grayed out .
Bul k Val ue Specifies t he bulk value for t he corresponding input
curve.
Bul k Val ue I ncl
L. E.
Specifies if a given bulk value cont ains t he
cont ribut ions of light ends. I f no light end composit ions
are given t hese checkboxes are grayed out .
Head% Specifies t he ending percent for t he head sect ion on
t he input basis.
Head Adj Wt Specifies t he corresponding relat ive bulk fit adj ust ing
weight fact or from 0 t o 10, where 0 means no
adj ust ing at all.
Mai n% Specifies t he ending percent for t he main sect ion of t he
input basis.
4- 21
When fit t ing a given bulk value, at least one sect ion must be
adj ust able. Ther efore, at least one sect ion must have a non- zero
percent age range and a non- zero adj ust ing weight fact or. Since t he
adj ust ing weight fact ors are relat ive, it is t he weight fact or rat ios
among t he t hree sect ions t hat mat t er.
The Appl y smar t bul k f i t t i ng on mol ecul ar w ei ght and mass
densi t y checkbox allows you t o achieve t he best bulk fit t ing on mass
densit y and molecular weight input curves. I f t he checkbox is select ed,
t he mass densit y and molecular weight rows are disabled and t he
values appear in black.
I n sit uat ions when eit her a full light ends analysis is not available or
you do not want t o ident ify part of t he analyzed light ends component s
( in ot her words, only part ial light ends analysis dat a is available) ,
UniSim Design can generat e overlapping hypot het ical component s t o
compensat e t he missing port ion of t he light ends, making t he out put
st ream mat ching bot h t he part ial light ends input and t he ot her input
curves. To act ivat e t his opt ion, select t he Al l ow Par t i al Li ght Ends
I nput checkbox. Once select ed, UniSim Design ident ifies t he need and
generat e t he needed hypot het ical component s t o compensat e t he
missing port ions of t he light ends, leading t o a much bet t er fit bet ween
t he generat ed curves and t he input curves.
I f t he input for eit her molecular weight or mass densit y curve is less
t han 95% on a user defined basis, only t he ext rapolat ed t ail is adj ust ed
t o mat ch t he user specified bulk value. I f t he input is more t han or
equal t o 95% on t he user defined basis, t he ent ire curve will be
adj ust ed t o mat ch t he bulk value specified.
The user input dat a is t he most reliable dat a available, and hence
should not be adj ust ed t o mat ch t he bulk value as long as t here is
enough ext rapolat ed dat a t o adj ust .
When only t he t ail is adj ust ed, it is ensured t hat t he upper end point is
no lower t han t he linear ext rapolat ion of t he last t wo point s. This
means t hat in most cases, t he ext rapolat ed por t ion of t he curve is
concave, i. e., t he curvat ure is posit ive. I f t he bulk value is given such
t hat t he ext rapolat ed values ar e below t he linear ext rapolat ion values,
t he whole cur ve is adj ust ed and t he following warning message is
displayed: Curve is normalized due t o t he inconsist ency bet ween t he
Mai n Adj Wt Specifies t he corresponding relat ive bulk fit adj ust ing
adj ust ing at all.
Tai l Adj Wt Specifies t he corresponding relat ive bulk fit adj ust ing
adj ust ing at all.
4- 22
supplied curve and bulk dat a.
I f t he upper limit value is reached when adj ust ing t he molecular weight
or densit y curve and t he specified bulk value is st ill not mat ched, no
adj ust ment is made and t he following message appears: No exact
mat ch, upper limit reached. For molecular weight , t he upper limit value
is t en t imes t hat of t he bulk value. For mass densit y, t he upper limit is
t hree t imes t hat of t he bulk value.
I f a bulk molecular weight or mass densit y is given wit hout a
corresponding input curve, t he whole calculat ed curve will be adj ust ed.
The 95% input is an art ificial dividing line t o decide if only t he t ail is
adj ust ed or t he whole curve is adj ust ed. I f t he user input curve crosses
t he dividing line, t here is a chance t o have a sudden change in t he
behaviour. I f t his occur s, you can overcome t he problem by manually
set t ing t he bulking fit t ing opt ions wit hout using t he smart opt ion. To
achieve similar result s manually, you can set t he Head Adj Wt and Main
Adj Wt t o zero, set t he Main % t o t he desired t ail st art ing percent , and
leave t he Tail Adj Wt t o it s default value of 1. 0.
Bulk Propert ies Definit ion
These bulk propert ies are opt ional except when dist illat ion dat a is not
available ( you have select ed None as t he Dat a Type) . I f you do not
supply any dist illat ion dat a, you must supply t wo of t he t hree init ial bulk
propert ies ( Molecular Weight , Mass Densit y or Wat son ( UOP) K fact or)
for UniSim Design t o creat e a "t ypical" TBP curve. This TBP curve is
generat ed based on a Whit son molar dist ribut ion model.
I f you are supplying propert y curves and you supply a bulk molecular
weight , densit y, or Wat son K fact or, UniSim Design smoot hes and
adj ust s t he corresponding curves t o mat ch t he supplied bulk propert ies.
This procedure is performed whet her you supply propert y curves or
t hey were int ernally generat ed by UniSim Design.
Assay Definit ion Group
The Assay Definit ion group cont ains only one obj ect involved in t he
specificat ion of Bulk Propert ies: t he Bulk Pr opert ies drop- down. The
4- 23
Bulk Propert ies drop- down list has t wo opt ions:
Used I f an Assay Dat a Type is not select ed, t he I nput Dat a group
displays t he Bulk Prop t able along wit h t he Molecular
Weight of light est component field. However, if an Assay
Dat a Type is select ed, a Bulk Props radio but t on appears in
t he I nput Dat a group. When t his radio but t on is act ive t he
Bulk Prop t able is displayed.
Not Used No bulk propert ies are considered in t he oil charact erizat ion
calculat ions.
4- 24
I nput Dat a Group
The I nput Dat a group t hat appears when Used is select ed for bulk
propert ies is shown in t he figure below:
I t consist s of t wo obj ect s: t he Bulk Propert ies t able and Molecular
Weight of light est component field.
The Bulk Propert ies t able has several fields:
Fi gur e 4. 13
The Mol ecul ar Wei ght of l i ght est component f i el d i s onl y
v i si bl e w hen t he Assay Dat a Type sel ect ed i s None.
Bul k Pr oper t i es Descr i pt i on
Mol ecul ar
Wei ght
The Molecular Weight must be great er t han 16.
St andar d Densi t y The mass densit y must be bet ween 250 and 2, 000 kg/
m
3
( unit s can be mass densit y, API , or specific gravit y,
chosen from t he drop- down list ) .
Wat son ( UOP) K
f act or
This fact or must be bet ween 8 ( highly aromat ic or
napht henic) and 15 ( highly paraffinic) . Only field unit s
are used here.
Bul k Vi scosi t i es The bulk viscosit y t ype and t he t emperat ure at t wo
reference point s.
high values
corresponding t o high
degrees of sat urat ion:
where:
Mean Avg. BP = t he
mean average
boiling point is in
degrees Rankine.
K
Mean Avg. BP
3
sp gr 60F / 60F
----------------------------- =
4- 25
Defining Assay Types
To define Assay t ypes, select a t ype in t he Assay Definit ion group using
t he drop- down list .
Assay t ypes t hat are available are described in t he t able below:
Fi gur e 4. 14
Assay Ty pe Descr i pt i on
TBP True boiling point dist illat ion dat a at at mospheric pressure.
Once you have select ed t his opt ion, t he TBP Dist illat ion
Condit ions group is displayed.
The default dist illat ion condit ions are at mospheric,
however, you can enable Vacuum Dist illat ion for sub-
at mospheric condit ions by act ivat ing t he Vacuum radio
but t on. The default pressure in t his case is 10 mmHg
( ASTM st andard) . When you supply sub- at mospheric dat a,
it is aut omat ically correct ed from vacuum t o at mospheric
condit ions using procedure 5A1. 13 ( wit hout K- correct ion)
from t he API Dat a Book.
ASTM D86 St andard ASTM D86 dist illat ion dat a at at mospheric
pressure.
You must provide dat a on a liquid volume basis.
ASTM D1160 ASTM D1160 dist illat ion dat a. Aft er you have select ed t his
opt ion, t he ASTM D1160 Dist illat ion Condit ions group is
displayed. By default , t he Vacuum radio but t on is select ed
and t he Vacuum Dist illat ion Pressure is set t o 10 mmHg
( ASTM st andard) . When ASTM D1160 Vacuum dat a is
supplied, UniSim Design will first convert it t o TBP vacuum
dat a, and t hen convert t his t o TBP dat a at 760 mmHg using
procedure 5A1.13 of t he API Dat a Book.
You must provide dat a on a liquid volume basis.
You can specify t he ASTM
D86/ TBP I nt erconversion
Met hod ( API 1974
1
, API
1987
2
, API 1994
3
or
Edmist er- Okamot o 1959
4
)
on t he Calculat ion Default s
t ab. Wit h t he ASTM D86
Assay t ype you can also
correct for t hermal
cracking as well as for
elevat ion.
4- 26
I nput Dat a Group
The I nput Dat a group displayed when t he Dist illat ion radio but t on is
select ed depends on t he Assay t ype you have select ed in t he Assay
Definit ion group.
Dist illat ion Dat a
For Assay Type opt ions TBP, ASTM D86, ASTM D1160, ASTM D2887 and
EFV, t he procedure for ent ering boiling t emperat ure informat ion is
essent ially t he same - you are required t o ent er at least five pairs of
Assay Percent s and boiling Temperat ures. The Dist illat ion input t able is
ASTM D86-
D1160
This is t he combinat ion of t he ASTM D86- D1160 dat a t ypes.
The opt ions for ASTM D86 and ASTM D1160 are similar t o
t he descript ions above. You must provide dat a on a liquid
volume basis.
ASTM D2887 Simulat ion dist illat ion analysis from chromat ographic dat a,
report ed only on a weight percent basis at at mospheric
pressure. On t he Calculat ion Default s t ab, you have t he
choice of conversion met hod ( API 1987
5
, API 1994
I ndirect
6
, API 1994 Direct
7
) .
Chr omat ogr a
ph
A gas chromat ograph analysis of a small sample of
complet ely vaporized oil, analyzed for paraffin, aromat ic
and napht henic hydrocarbon groups from C
6
t o C
30
.
Chromat ographic analyses may be ent ered on a mole,
mass, or liquid volume basis. Wit h t his opt ion, you ent er
Light Ends, Bulk and Chromat ographic analysis dat a. ( See
Chr omat ogr aphi c Assay I nput below) .
EFV Equilibrium flash vaporizat ion curve; t his involves a series
of experiment s at const ant at mospheric pressure, where
t he t ot al vapour is in equilibrium wit h t he unvaporized
liquid.
None No dist illat ion dat a is available; UniSim Design generat es a
TBP curve from bulk propert y dat a. Wit h t his opt ion, you
only ent er bulk dat a.
Assay Ty pe Descr i pt i on
The conversion procedure
from various assay t ypes
t o a TBP curve is based
on Fi gur e 3- 0. 3 of t he
API Dat a Book.
4- 27
exact ly t he same for each of t hese opt ions.
For t he ASTM D86- D1160 charact erizat ion procedure, you are requir ed
t o ent er boiling t emperat ure informat ion for bot h t he ASTM D86 and
ASTM D1160 dat a t ypes. This procedure averages t he ASTM D86 cur ve
and ASTM D1160 curve in t he area where t hey overlap.
For example, in t he combined ASTM D86- D1160 input form shown on
t he figure below, t he last recorded ASTM D86 assay point is at 30 vol%,
and t he first report ed ASTM D1160 dat a point is at 10 vol%.
Fi gur e 4. 15
You can v i ew and edi t t he assay boi l i ng Temper at ur e i nput
t abl e by sel ect i ng t he Di st i l l at i on r adi o but t on and cl i ck i ng
t he Edi t Assay but t on.
Fi gur e 4. 16
4- 28
Therefor e, t he result ing TBP curve will represent t he average of t he t wo
curves bet ween 10 vol% and 30 vol%. Each curve must cont ain a
minimum of 5 dat a point s.
Chromat ographic Assay I nput
This dist illat ion opt ion allows you t o ent er a st andard laborat ory
chromat ographic analysis direct ly. The only requir ed input is t he assay
fract ion for each chromat ographic hydrocarbon group in t he paraffin,
aromat ic, and napht henic families. The required minimum of five point s
can be any combinat ion of point s from t he t hree PNA groups. The
normal boiling point of each hydrocarbon group is displayed in t he PNA
t ables.
Chromat ographic analyses may be ent ered on eit her a mole, mass, or
liquid volume basis, wit h t he best result s obt ained when t he input
fract ions are on a mole fract ion basis.
A t ypical C
6+
liquids chromat ographic analysis is shown in t he
chromat ographic input form below.
Chromat ographic analyses are t ypically performed aft er t he light ends
of t he original sample are removed. I f you have a Light Ends analysis in
t his case, refer t o Li ght Ends Handl i ng & Bul k Fi t t i ng for det ails.
Fi gur e 4. 17
You may also supply bulk
propert y dat a ( see Bulk
Propert ies in Sect i on
4.5. 1 - I nput Dat a Tab
for det ails) .
4- 29
Assay I nput - No Dist illat ion Dat a Available
When a dist illat ion analysis is not available, UniSim Design generat es a
t ypical TBP curve based on supplied bulk propert ies ( molecular weight ,
mass densit y, and Wat son ( UOP) K fact or ) . You have t he opt ion of
specifying t he molecular weight of t he light est component in t he
mixt ure, which may help in generat ing more accurat e TBP curves for
heavy pet roleum fluids.
Alt hough accurat e enough for heat balance applicat ions, caut ion should
be exercised when t he Whit son opt ion is used t o produce
hypocomponent for fract ionat ion calculat ions. This met hod realist ically
supplies accuracy sufficient only for pr eliminary sizing calculat ions.
For condensat e wit h only bulk dat a available for t he C
7+
fract ion,
experience has shown a considerable increase in accuracy by
represent ing t he fract ion wit h several hypocomponent as opposed t o a
single hypot het ical component wit h t he bulk propert ies.
Refer t o Bul k Pr oper t i es Def i ni t i on ( earlier in t his Sect ion) for det ails
on ent ering bulk propert y dat a, part icularly in regards t o Bulk
Viscosit ies.
General Guidelines
Some general guidelines are provided below:
There is no limit t o t he number of assay dat a point s t hat you
may ent er for TBP, ASTM D86, ASTM D1160, ASTM D86- D1160
ASTM D2887 or EFV analyses. Dat a point s may be input in any
order, as UniSim Design aut omat ically sort s your input dat a.
UniSim Design requires a minimum of 5 dat a point s for all
assays. Depending on t he shape of t he input curve, int ermediat e
values for UniSim Design' int ernal TBP working curve are
int erpolat ed using eit her a t hird or fourt h order LaGrange
polynomial fit . The point s out side your dat a are ext rapolat ed
using t he ext rapolat ion met hod which you select on Calculat ion
Default s t ab: Least Squares, Lagrange or Probabilit y.
Fi gur e 4. 18
UniSim Design uses t he
Whit son Molar
Dist ribut ion model t hat
requires at least t wo of
t he t hree bulk propert ies
( not including bulk
viscosit ies) t o produce an
average TBP dist ribut ion.
4- 30
Each t ime you change t he Basis or Ext rapolat ion met hod, t he
Assay needs t o be recalculat ed.
TBP, EFV, and Chromat ographic laborat ory assay values may be
ent ered on a liquid volume, mole or weight basis. Liquid volume
is t he default basis for TBP and EFV input , and mole is t he
default basis for Chromat ographic input . Due t o t he form of t he
conversion curves in t he API Dat a Book, you must supply your
ASTM D86 and ASTM D1160 dist illat ion dat a on a liquid volume
basis. ASTM D2887 is only report ed on a weight percent basis.
I f you are edit ing an assay, redefining t he Basis does not alt er
your supplied assay values. For example, consider an assay
curve wit h 10, 30, 50, 70 and 90 liquid volume percent point s. I f
you change t he Basis t o mass percent , t he assay percent s and
t emperat ure are not changed. The t emperat ure you supplied for
10% liquid volume is ret ained for 10% mass.
Light Ends Definit ion
Light Ends are defined as pure component s wit h low boiling point s.
Component s in t he boiling range of C
2
t o n- C
5
are most commonly of
int erest . Generally, it is preferr ed t hat t he port ion of t he oil' s dist illat ion
assay below t he boiling point of n- C
5
be replaced wit h discret e pure
component s ( library or hypot het ical) . This should always yield more
accurat e result s t han using hypocomponent t o represent t he Light Ends
port ion.
UniSim Design provides t hree opt ions t o account for Light Ends, which
are as follows:
Uni Si m Desi gn gener at es al l of i t s phy si cal and cr i t i cal
pr oper t i es f r om an i nt er nal l y gener at ed TBP cur v e at
at mospher i c condi t i ons. Regar dl ess of w hat t y pe of assay
dat a you pr ovi de, Uni Si m Desi gn al w ays conver t s i t t o an
i nt er nal TBP cur ve f or t he char act er i zat i on pr ocedur e. The
i nt er nal TBP cur ve i s not st or ed w i t h t he assay .
I gnor e UniSim Design charact erizes t he Light Ends port ion of your
sample as hypocomponent s. This is t he least accurat e
met hod and as such, is not recommended.
Aut o
Cal cul at e
Select t his when you do not have a separat e Light Ends
analysis but you want t he low boiling port ion of your assay
represent ed by pure component s. UniSim Design only uses
t he pure component s you select ed in t he fluid package.
I nput
Composi t i on
Select t his when you have a separat e Light Ends assay and
your pet roleum assay was prepared wit h t he light ends in
t he sample. UniSim Design provides a form list ing t he pure
component s you select ed in t he fluid package. I nput your
dat a on a non- cumulat ive basis.
4- 31
The following sect ions provide a det ailed explanat ion of Light Ends, how
t he laborat ory may account for t hem, how t hey ar e r eport ed and how
UniSim Design ut ilizes t his informat ion. I t is recommended t hat you
read t his informat ion t o ensure t hat you are select ing t he right opt ions
for your assay.
Laborat ory Assay Preparat ion
During TBP and ASTM laborat ory dist illat ions, loss of some of t he Light
Ends component s from t he sample fr equent ly occurs. To provide
increased accuracy, a separat e Light Ends assay analyzed using
chromat ographic t echniques may be report ed.
Regardless of whet her a separat e light ends analysis was provided,
your overall assay is eit her Light Ends I ncluded or Light Ends Free. The
way in which your sample was analyzed affect s bot h t he result s and t he
met hod you should use t o input t he informat ion for your
charact erizat ion.
Light Ends Port ion I ncluded in Assay
I n t his case, your assay dat a was obt ained wit h t he light ends
component s in t he sample; i. e., t he assay is for t he whole sample. The
I BP t emperat ure for your assay is lower t han t he boiling point of t he
heaviest pure light end component . This corresponds t o an I BP
approximat ely equal t o t he weight ed average boiling point of t he first
1% of t he overall sample. For example, if t he light est component is
propane and it makes up more t han 1% of t he t ot al sample, t he I BP of
t he assay is approximat ely - 45F ( t he normal boiling t emperat ure of
propane) .
I f t he Light Ends were included in your overall assay, t here are t wo
To cor r ect l y empl oy t he Aut o Cal cul at e or I nput Composi t i on
opt i ons, y ou shoul d ei t her pi ck l i br ar y component s, or def i ne
hypot het i cal component s t o r epr esent t he Li ght Ends bef or e
ent er i ng t he Oi l Char act er i zat i on env i r onment . I f y ou hav e
sel ect ed t he Aut o Cal cul at e met hod w i t hout speci f y i ng l i ght
ends, Uni Si m Desi gn cal cul at es t he oi l usi ng onl y
hypocomponent , j ust as i f you had sel ect ed I gnor e. I f you
sel ect ed I nput Composi t i on, t her e ar e no l i ght end
component s f or w hi ch y ou can suppl y composi t i ons. You can
go back t o t he Fl ui d Pack age vi ew at any t i me and def i ne
y our l i ght component s.
4- 32
possibilit ies:
Assay is Light Ends Free
Your assay dat a was analyzed wit h t he Light Ends component s removed
from t he sample, or t he assay was already adj ust ed for t he Light Ends
component s. The I BP t emperat ur e for your assay is higher t han t he
boiling point of t he heaviest pure light end component - t ypically your
assay is for t he C
6+
fract ion only and t he I BP t emperat ure is somewhat
above 95F ( 36C) .
I f your dist illat ion dat a is light - ends fr ee and you have separat e light -
ends analysis dat a, you can use UniSim Design oil charact erizat ion t o
combine t he t wo. The advant age of doing t his is t hat t he bulk
propert ies, if available, will be fit t ed and mat ched accurat ely. To do t he
combining, you need t o input t he dist illat ion dat a and light ends dat a as
usual and t hen click t he Li ght Ends Handl i ng & Bul k Fi t t i ng Opt i ons
but t on accessible from I nput Dat a or User Cur v es t ab. I n t he Light -
Ends Handling & Bulk Fit t ing Opt ions view, uncheck t he Cur v e I ncl L.E.
checkbox for dist illat ion. I f you have bulk propert ies t o fit , you need t o
indicat e if t he bulk values include light ends by checking or unchecking
t he Bul k Val ue I ncl L. E. checkboxes.
I nput Dat a Group
When you have select ed I nput Composit ion as t he Light Ends opt ion
and you select t he Light Ends radio but t on in t he I nput Dat a group, t he
Li ght Ends
Anal y si s
Suppl i ed
I f you know t hat light ends are included in your assay,
select t he I nput Composi t i on opt ion from t he Light
Ends group, and ent er t he composit ion dat a direct ly
int o t he Light Ends composit ion view.
No Li ght Ends
Anal y si s
Av ai l abl e
I f you do not have a laborat ory analysis for t he light
ends port ion of your assay, t hen you should use t he
Aut o Calculat e opt ion. UniSim Design represent s t he
light ends port ion of your assay as discret e pure
component s, aut omat ically assigning an appropriat e
assay percent age t o each. I f you do not do t his ( you
select I gnore) , UniSim Design represent s t he Light
Ends port ion of t he assay as pet roleum
hypocomponent .
4- 33
following view appears.
There are t hree obj ect s associat ed wit h t he Light Ends I nput and are
described below:
Fi gur e 4. 19
Li ght Ends Basi s Allows you t o select t he basis for t he Light Ends
analysis on a mole, mass, or liquid volume basis. The
way in which you ent er t he rest of t he light ends dat a
depends on whet her you select a percent or flow basis:
Per cent . Ent er t he percent composit ions for t he
Light Ends on a non- cumulat ive basis. UniSim
Design calculat es t he t ot al Light Ends percent age
by summing all of t he Light Ends assay dat a. I f
t he sum of t he light ends assay values is equal t o
100 ( you have submit t ed normalized dat a) , you
must ent er t he Percent of light ends in t he Assay.
This value must be on t he same basis as t he
dist illat ion dat a.
I f t he sum of t he light ends is equal t o 1. 0000,
UniSim Design assumes t hat you have ent ered
fract ional dat a ( rat her t han percent ) , and you are
required t o ent er t he Percent of light ends in t he
Assay.
Fl ow . Ent er t he flows for each component , as well
as t he percent of light ends in t he assay.
4- 34
Aut o Calculat e Light Ends
The Aut o Calculat e ext ract ion procedure int ernally plot s t he boiling
point s of t he defined Light Ends component s on t he TBP working curve
and det ermine t heir composit ions by int erpolat ion. UniSim Design
adj ust s t he t ot al Light Ends fract ion such t hat t he boiling point of t he
heaviest Light End is at t he cent roid volume of t he last Light Ends
component . The result s of t his calculat ion are displayed in Light Ends
Composit ion mat rix.
I f a fluid package cont ains a large number of hydr ocarbons, especially
heavy ones, UniSim Design may allocat e a very large port ion of t he
assay input t o light ends, leading t o undesired result s. The checkboxes
under t he Use column allows you t o decide which component s are used
in t he light ends aut o allocat ion. This opt ion gives you more cont rol on
t he light ends t o be used, and allows t he use of any fluid package t o be
associat ed wit h t he oil manager, even wit h very heavy hydrocarbons.
Li ght Ends
Composi t i on
mat r i x
The mat rix consist s of t he t hree fields:
Li ght Ends. Displays all pure component s or
hypot het icals you select ed in t he associat ed fluid
package.
Composi t i on. The composit ion value of t he
associat ed component is eit her ent ered ( when
Light Ends drop- down is set t o I nput
Composi t i on) or aut omat ically calculat ed ( when
t he Light Ends drop- down is set t o Aut omat ically
Calculat ed)
NBP. The Normal Boiling Point of t he associat ed
component or hypot het ical.
Per cent of l i ght s
ends i n Assay
The t ot al percent age of light ends in t he Assay. I f t he
Light Ends Basis select ed is percent age ( i. e.,
LiquidVolume%, Mole% or Mass%) , t hen t his is
aut omat ically calculat ed. I f t he Basis select ed is flow
based ( i. e., Liquid Flow, Mole Flow or Mass Flow) , you
are required t o provide t his value.
Refer t o Appendi x B -
Oi l Met hods &
Cor r el at i ons for a
graphical represent at ion
of t he Aut o Calculat e
Light Ends removal
procedure.
4- 35
Unlike when set t ing t he I nput Composit ion, t he mat rix is not edit able.
Physical Propert y Curves Specificat ion
Physical proper t y analyzes are nor mally report ed from t he laborat ory
using one of t he following t wo convent ions:
An I ndependent assay basis, where a common set of assay
fract ions is not used for bot h t he dist illat ion curve and physical
propert y cur ve.
A Dependent assay basis, where a common set of assay
fract ions is used for bot h t he dist illat ion curve and t he physical
propert y cur ves.
Physical proper t ies are average values for t he given range, and hence
are midpoint values. Dist illat ion dat a report s t he t emperat ure when t he
last dr op of liquid boils off for a given assay range, and t herefore
dist illat ion is an endpoint propert y. Since all dependent input propert y
curves are report ed on t he same endpoint basis as t he dist illat ion
curve, t hey are convert ed by UniSim Design t o a midpoint basis.
I ndependent propert y curves ar e not alt ered in any manner as t hey ar e
already defined on a midpoint basis.
As wit h dist illat ion curves, t here is no limit t o t he number of dat a point s
you provide. The order in which you input t he point s is not import ant ,
as UniSim Design sort s t he input dat a. A minimum of five dat a point s is
required t o define a propert y curve in UniSim Design. I t is not
necessary t hat each propert y curve point have a corr esponding
Fi gur e 4. 20
4- 36
dist illat ion value.
I f a bulk molecular weight or mass densit y is going t o be supplied, t hen
t he corresponding Molecular Weight or Densit y working curve
generat ed from your input is smoot hed t o ensure a mat ch. I f you do not
ent er bulk proper t ies, t hen t hey ar e calculat ed from t he unsmoot hed
working curves.
Each propert y curve t ype ( i. e., Molecular Wt ., Densit y and Viscosit y)
has it s own drop- down list in t he Assay Definit ion group.
Each drop- down list cont ains t he same t hree opt ions and are described
below:
I nput Dat a Group
Defining Molecular Weight and Densit y pr opert y curves as eit her
I ndependent or Dependent adds t he corresponding radio but t on t o t he
I nput Dat a group. However, defining a Viscosit y propert y curve as
I ndependent or Dependent , UniSim Design accept s viscosit ies for assay
values at t wo specified t emperat ures, wit h t he default t emperat ures
Ent er i ng t he 0 vol % poi nt of a dependent cur v e cont r i but es
t o def i ni ng t he shape of t he i ni t i al por t i on of t he cur v e, but
has no phy si cal meani ng si nce i t i s a mi dpoi nt pr oper t y
cur v e.
Fi gur e 4. 21
Not Used No propert y dat a is considered in t he assay calculat ion.
Dependent A common set of assay fract ions is used for bot h t he
dist illat ion curve and t he physical propert y curves.
I ndependent A common set of assay fract ions is not used for bot h t he
dist illat ion curve and physical propert y curve.
4- 37
being 100 and 210F. Act ivat ing t he Molecular Wt ., Densit y, Viscosit y1
or Viscosit y2 radio but t ons brings up t he obj ect s associat ed wit h t he
specificat ion of t he respect ive propert y curve.
To ent er t he propert y curve dat a, simply select t he radio but t on for t he
propert y curve you want t o input and click t he Edit Assay but t on.
Molecular Wt . Curve
An example of a Molecular Weight assay is shown below:
The assay dat a is ent ered int o t he Assay I nput Table view which is
opened when t he Edit Assay but t on is select ed. The form of t his view is
t he same regardless of whet her you have specified I ndependent or
Dependent dat a. However, if you specified Dependent dat a, t he Assay
Percent s t hat you defined for t he dist illat ion dat a are aut omat ically
ent ered in t he t able.
Depending on t he shape of t he curve, int ermediat e values for UniSim
Design' int ernal working curve are int erpolat ed using eit her a t hird or
fourt h order Lagrange polynomial fit of your input curve, while point s
out side your dat a are ext rapolat ed. You can select t he ext rapolat ion
met hod for t he fit of your input curve on t he Calculat ion Default s t ab:
Least Squar es, Lagrange or Probabilit y.
Fi gur e 4. 22
I n Dependent Curves,
making a change t o an
Assay Percent value
aut omat ically changes
t his value in all ot her
Dependent curves
( including t he Boiling
Point curve) .
4- 38
Densit y Curve
An example of a Densit y assay is shown below:
The assay dat a is ent ered int o t he Assay I nput Table view which is
opened when t he Edit Assay but t on is select ed. The form of t his view is
t he same regardless of whet her you have specified I ndependent or
out side your dat a are ext rapolat ed. You may select t he ext rapolat ion
Least Squar es, Lagrange ( default ) or Probabilit y.
Viscosit y Curves
UniSim Design accept s viscosit ies for assay dat a at t wo specified
t emperat ures and t herefore pr ovides t wo radio but t ons, Viscosit y1 and
Fi gur e 4. 23
4- 39
Viscosit y2, in t he I nput Dat a group.
You can input dat a for one or bot h of t he viscosit y curves. Each radio
but t on brings up ident ical set s of obj ect s, specific t o assay dat a at t he
designat ed t emperat ure. Temperat ures are ent ered in t he Temperat ure
field wit h default values being 100 and 210F. This implies t hat you
have det ermined t he viscosit y at 100 or 210F for each of your assay
port ions ( 10%, 20%, et c. ) .
I n t he Viscosit y Curves group box, you can specify which curve ( or
bot h) you want t o use by select ing t he appropriat e radio but t on.
The Assay I nput Table view, which is opened when t he Edit Assay
but t on is select ed, is filled in wit h t he assay dat a. The form of t his view
is t he same regardless of whet her you have specified I ndependent or
You may also define t he viscosit y unit t ype. The Unit s Type can be one
of t he following:
out side your dat a are ext rapolat ed. You may select t he ext rapolat ion
Least Squar es, Lagrange or Probabilit y.
The default s for a new assay may be modified by clicking t he Oi l I nput
Pr ef er ences but t on on t he Assay t ab of t he Oil Charact er izat ion
Fi gur e 4. 24
Uni t Ty pe Descr i pt i on
Dy nami c Convent ional viscosit y unit s ( e. g., - cP)
Ki nemat i c Rat io of a fluid' s viscosit y t o it s densit y ( e. g., - st oke, m
2
/ s)
4- 40
view. The same view may also be accessed from t he Simulat ion
environment by t he following sequence:
1. Select Tool s- Pr ef er ences command fr om t he menu bar.
2. On t he Session Prefer ences view, go t o t he Oi l I nput t ab.
3. Select t he Assay Opt i ons page.
4. 5. 2 Calculat ion Default s Tab
The Calculat ion Default s t ab is shown below:
The int ernal TBP curve is not st ored wit h t he assay. The Calculat ion
Default s t ab cont ains t hree main gr oups:
Conver sion Met hods
Correct ions for Raw Lab Dat a
Ext rapolat ion Met hods
Conversion Met hods Group
UniSim Design generat es all of it s physical and crit ical propert ies fr om
an int ernally generat ed TBP curve at at mospheric condit ions.
Regardless of what t ype of assay dat a you provide, UniSim Design
always convert s it t o an int ernal TBP curve for t he charact erizat ion
procedure. For ASTM D86 and ASTM D2887 assays t ypes, you may
specify t he int er- conver sion or conversion met hods used in t he
Conver sion Met hods group.
Fi gur e 4. 25
4- 41
The group consist s of t he following t wo drop- down list s:
Correct ions for Raw Lab Dat a Group
I n t his group, t wo correct ion met hods are available for previously
uncorrect ed laborat ory dat a:
Ext rapolat ion Met hods Group
UniSim Design allows you t o choose t he ext rapolat ion met hod used for
t he different Assays ( i. e., Dist illat ion and t he Molecular Weight , Densit y
Fi el d Descr i pt i on
D86- TBP
( I nt er conv er si on)
There are four int erconversion met hods available:
API 1974
1
API 1987
2
API 1994
3
Edminst er Okamot o 1959
4
D2887- TBP
( I nt er conv er si on)
There are t hree int erconversion met hods
available:
API 1987
5
API 1994 I ndirect
6
API 1994 Direct
7
Cor r ect i on Descr i pt i on
Appl y Lab
Bar omet r i c
Pr essur e
Cor r ect i on
ASTM D86 dat a t hat is generat ed above sea level
condit ions must be correct ed for baromet ric pressure.
I f t his is not done by t he laborat ory, select t he Yes
radio but t on from t he subgroup and UniSim Design
performs t he necessary correct ions. Ent er t he ambient
laborat ory baromet ric pressure in t he Lab Baromet ric
Pressure field and UniSim Design correct s your ASTM
dist illat ion dat a t o 1at m before applying t he API Dat a
Book conversions for ASTM D86 t o TBP dist illat ion.
Appl y ASTM D86
API Cr ack i ng
Cor r ect i on
API no longer recommends using t his correct ion:
The ASTM cracking correct ion is designed t o correct for
t he effect s of t hermal cracking t hat occur during t he
laborat ory dist illat ion. I f t his is not done by t he
laborat ory, select t he Yes radio but t on, and UniSim
Design performs t he necessary correct ions. This
correct ion is only applied t o ASTM D86 t emperat ures
great er t han 485F ( 250C) .
The API cracking correct ion should not be applied t o
ASTM D86 dist illat ions t hat ext end beyond 900F
( 500C) , due t o t he exponent ial nat ure of t he
correct ion.
4- 42
and Viscosit y pr opert y curves) . There are t hree met hods available:
This group also allows you t o specify which end of t he curve t o apply
t he ext rapolat ion met hod. There are t hree choices available:
Upper end
Lower end
Bot h ends
4. 5. 3 Working Curves Tab
The t hird t ab of t he Assay view is t he Wor k i ng Cur v es t ab. Aft er t he
Ex t r apol at i on
Met hod
Uses
Lagr ange For assays represent ing cut s ( i. e., napht ha) or assays
for propert ies ot her t han Boiling Temperat ure.
Least Squar es The Least Squares met hod is a lower order Lagrange
met hod. For t his met hod, t he last five input point s are
used t o fit a second order polynomial. I f t he curvat ure
is negat ive, a st raight line is fit .
Pr obabi l i t y Use t he Probabilit y ext rapolat ion met hod in cases when
your Boiling Temperat ure assay represent s a full range
crude and t he dat a is relat ively flat . For inst ance, t he
dat a in t he dist illat ion range of your assay ( i. e., 10% t o
70%) may be relat ively const ant . I nst ead of linearly
ext ending t he curve t o t he I BP and FBP, t he Probabilit y
met hod only considers t he st eep rise from t he FBP.
T
e
m
p
e
r
a
t
u
r
e
Assay%
Known Part
of Curve
Ext rapolat ed
Part
4- 43
Assay is calculat ed, you can view t he Assay Working Curves:
Recall t hat t he working curves are int erpolat ed using eit her a t hird or
fourt h order Lagrange polynomial fit of your input curve, while t he
met hod used t o ext rapolat e point s out side your dat a depends on t he
t ype of curve ( Mass Densit y, Viscosit y, Molecular Weight ) . You select
t he met hod for t he fit of your input curve: Least Squares, Lagrange or
Probabilit y.
UniSim Design always uses 50 point s in t he calculat ion of t he wor king
curves, but t he molar dist ribut ion varies depending on t he dat a you
provide. I n cases where t here is a region wit h a st eep gradient , UniSim
Design moves more point s t o t hat region, but st ill uses 50 point s.
4. 5. 4 Plot s Tab
Following t he Working Curves t ab is t he Plot s t ab, on which you can
view any of t he input dat a curves in a graphical format .
The Propert y drop- down list , shown above, displays t he opt ions
available for t he y- axis of t he plot . The Dist illat ion opt ion shows t he
Fi gur e 4. 26
Fi gur e 4. 27
4- 44
boiling t emperat ure input according t o t he Assay Type chosen ( i. e., TBP,
ASTM D86, et c. ) . The x- axis displays t he Assay% on a basis consist ent
wit h t he format of your input .
An example of a dist illat ion boiling point curve is shown in t he figure
below. All of t he ent ered dat a point pair s and t he int erpolat ed values
are drawn on t he plot .
To make changes t o t he appearance of t he plot , obj ect inspect t he plot
area. From t he menu t hat appears, select Graph Cont rol.
4. 5. 5 Correlat ions Tab
The Corr elat ions t ab of t he Assay propert y view is shown below:
Fi gur e 4. 28
Fi gur e 4. 29
The User Pr oper t y
opt ion is only available if
a User Propert y is
creat ed and a User
Curve is defined in t he
Assay.
For det ails on t he various
Graph Cont rol opt ions,
refer t o Sect i on 10. 4 -
Gr aph Cont r ol of t he
Uni Si m Desi gn User
Gui de.
4- 45
The correlat ions t ab consist s of t he following obj ect s:
Only t he molecular weight and specific gravit y correlat ions are requir ed
in t he calculat ion of t he wor king curves. The crit ical pressure, crit ical
t emperat ure, acent ricit y, and ideal gas ent halpy correlat ions are also
displayed on t he Assay propert y view, as t hese are applicable only in
t he calculat ion of t he hypocomponent propert ies.
I f you supply molecular weight or densit y curves, t hen t heir respect ive
correlat ions are not required. You do not have a choice of correlat ions
for calculat ing t he viscosit y curves.
Sel ect ed
Cor r el at i on
Set
By default , t his is Default Set ( if you have changed t he
name of t he default set , t hat name is displayed) . You can
select anot her correlat ion set from t he Select ed drop- down
list , but first you must define one on t he Correlat ion t ab of
t he Oil Charact erizat ion propert y view.
Low and
Hi gh End
Temper at ur e
This is t he range for which t he Correlat ions are applied. I f
you split t he range, t hen more t han one t emperat ure range
is displayed.
You can edit t he t emperat ure of defined split s for cust om
Correlat ion Set s on t his t ab.
MW The MW correlat ion is displayed. You cannot change t he
correlat ion in t his view; t his can be done from t he
Correlat ion t ab accessible from t he main Oil
Charact erizat ion view or by clicking t he Edit but t on.
You can change only t he name of t he default set . I f you
want t o change any correlat ions, you must creat e a new
correlat ion set .
SG The specific gravit y ( densit y) correlat ion is displayed. You
cannot change t he correlat ion in t his view; t his can be done
from t he Correlat ion t ab accessible from t he main Oil
Tc, Pc, Acc.
Fact or , I deal
H
The crit ical t emperat ure, crit ical pressure, acent ricit y and
I deal Gas Ent halpy correlat ions are displayed. You cannot
change correlat ions on t his t ab; t his can be done in t he
Correlat ion view accessible from t he main Oil
Charact erizat ion view. To edit t he Select ed Correlat ion Set
from t his t ab, click t he Edit but t on. This t akes you t o t he
Correlat ion view.
Al t hough a Cor r el at i on set cont ai ns met hods f or al l
pr oper t i es, t he Cor r el at i on t ab, as seen on t he Assay and
Bl end v i ew s, di spl ay s onl y t he pr oper t i es appr opr i at e t o t hat
st ep i n t he Char act er i zat i on pr ocess.
You can define new
correlat ions set s via t he
Correlat ion t ab,
accessible from t he main
Oil Charact erizat ion
view. See Sect i on 4.8. 1
- Cor r el at i on Tab.
4- 46
4. 5. 6 User Curves Tab
The User Curves t ab of t he Assay propert y view is shown below:
The available and select ed User Proper t ies are displayed in t he left
port ion of t he view. User Pr opert ies are defined on t he User Propert y
t ab of t he Oil Charact erizat ion view.
Aft er a User Propert y is defined, you can add it t o t he Assay by
highlight ing it and select ing t he Add but t on. To remove a User Propert y
from t he current Assay, highlight it and select t he Remove but t on.
Double- clicking on a User Propert y name in t he select ion list opens t he
user propert y view as described in Sect i on 4. 7.2 - User Pr oper t y
Vi ew .
Aft er adding a User Propert y, you can edit t he User Curve Dat a:
Fi gur e 4. 30
User Cur v e Dat a Descr i pt i on
Tabl e Ty pe This is eit her Dependent or I ndependent . I f you select
Dependent , t he Assay Percent s are aut omat ically set t o
t he values you specified for t he Boiling Temperat ure
assay ( I nput Dat a t ab) .
I f t he t able t ype is Dependent and you change t he
assay percent s on t his t ab, t his also changes t he assay
percent s in t he Dist illat ion boiling t emperat ure mat rix
and for any ot her dependent curve.
Bul k Val ue Specify a Bulk Value. I f you do not want t o supply a
bulk value for t he user propert y, ensure t hat t his cell
reads < empt y> by placing t he cursor in t hat cell and
pressing t he DELETE key.
See Li ght Ends
Handl i ng & Bul k Fi t t i ng
for det ails on t he Light
Ends Handling & Bulk
Fit t ing Opt ions but t on.
There are t wo element s t o
a User Curve:
The definit ion of how
t he propert y value is
calculat ed for a
st ream ( mixing rule) .
The assay/ propert y
value informat ion
t hat is supplied for a
given assay.
The propert y definit ion
( see Sect i on 4.7 - User
Pr oper t y for det ails) is
common t o all assays.
4- 47
4. 5. 7 Not es Tab
UniSim Design provides a t ab where you can ent er a descript ion of t he
Assay for your own fut ure reference. This can also be accessed t hr ough
t he not es manager.
4. 6 Hypocomponent
Generat ion
The Cut / Bl end t ab of t he Oil Charact erizat ion view is shown below:
The Available Blends are list ed in t he left port ion of t he view. The
Ex t r apol at i on
Met hod
This field allows you t o choose t he ext rapolat ion
met hod used for t he select ed user propert y in t he
current assay. The available choices are:
Least Squares
Lagrange
Probabilit y
Appl y To This field allows you t o choose which end of t he curve
t o apply t he ext rapolat ion met hod t o. There are t hree
choices available:
Upper end
Lower end
Bot h ends
User Pr oper t y
Tabl e
Provide t he Assay percent s and User Propert y Values in
t his t able. At least five pairs of dat a are required.
Fi gur e 4. 31
User Cur v e Dat a Descr i pt i on
For a highlight ed Blend,
you can edit t he name
and provide a descript ion
in t he Blend I nformat ion
group.
4- 48 Hy pocomponent Gener at i on
4- 48
following Blend manipulat ion but t ons are available:
I n t he following sect ions, each t ab of t he Blend propert y view ( accessed
t hrough t he View or Add but t ons) is described.
4. 6. 1 Dat a Tab
The Cut / Blend charact erizat ion in UniSim Design split s int ernal working
curves for one or more assays int o hypocomponent s. Once your assay
informat ion is ent ered t hrough t he Assay view, you must Add a Blend
and t ransfer at least one Assay t o t he Oil Flow I nformat ion t able t o split
t he TBP working curve( s) int o discret e hypocomponent . The first t ab of
t he Blend view is shown below:
Assay Select ion
A list of t he available Assays is shown in t he left port ion of t he view. You
can choose an assay by highlight ing it and clicking t he Add but t on. I t is
removed from t he Available Assays list and added t o t he Oil Flow
Vi ew Edit t he current ly highlight ed Blend.
Add Creat e a new Blend.
Del et e Erase t he current ly highlight ed Blend. UniSim Design does
not prompt for confirmat ion when delet ing a Blend, so be
careful when you are using t his command.
Cl one Creat e a new Blend wit h t he same propert ies as t he
current ly highlight ed Blend. UniSim Design immediat ely
opens a new Blend view.
Fi gur e 4. 32
As described in t he Oil
Charact erizat ion View
sect ion:
The Cl ear Al l but t on
is used t o delet e all
informat ion.
The Cal cul at e Al l
but t on recalculat es
all Assay and Blend
informat ion.
The Oi l Out put
Set t i ngs... but t on
allows you t o change
I BP, FBP, ASTM D86,
and ASTM D2887
int erconversion
met hods for out put
relat ed calculat ions.
All Boiling Point
informat ion supplied in an
assay is convert ed t o TBP
format .
To view an Assay, double-
click on t he Assay name,
eit her in t he Available
Assays list , or in t he Oil
column of t he Oil Flow
I nformat ion t able.
4- 49
I nformat ion t able, which displays t he following informat ion:
You can remove an Assay from t he Oil Flow I nformat ion t able by
highlight ing it and select ing t he Remove but t on.
Bulk Dat a
The Bulk Dat a but t on becomes available when more t han one assay is
present in t he Oil Flow I nfor mat ion t able.
UniSim Design allows you t o provide t he following bulk dat a for a blend
on t he Bulk Values view:
Molecular Weight
Mass Densit y
Wat son ( UOP) K
Viscosit ies at 2 t emperat ures
The Bulk Dat a feat ure is part icularly useful for supplying t he bulk
viscosit ies of t he blend, if t hey ar e known.
Oi l Fl ow I nf or mat i on Descr i pt i on
Oi l The name of t he Assay is displayed in t his column.
There is no limit at ion t o t he number of assays t hat
can be included in a single blend or t o t he number
of blends t hat can cont ain a given assay. Each
blend is t reat ed as a single oil and does not share
hypocomponent wit h ot her blends or oils.
Fl ow Uni t s You can select t he Flow Basis ( Mole, Mass or Liquid
Volume) here.
I f you have several Assays, it is not necessary t hat
t hey have t he same Flow Basis.
Fl ow Rat e Ent er t he flow rat e; you can use any unit s ( wit h
t he same basis) ; t hey are convert ed t o t he
default .
You are allowed t o define a flowsheet st ream for
each const it uent assay in a blend.
Fi gur e 4. 33
4- 50
Cut Ranges
You have t hr ee choices for t he Cut Opt ion Select ion:
These met hods are described in det ail lat er in t his sect ion.
You can specify as many component s as you want , wit hin t he
limit at ions of t he available memory. Whet her specified or calculat ed
int ernally, each cut point is int egrat ed t o det ermine t he average
( cent roid) boiling point . The cent roid is always det ermined using
UniSim Design' int ernally generat ed TBP curve on a weight basis.
Alt hough t he ext ernal procedure for blending assays is almost ident ical
wit h t hat for cut t ing a single assay, UniSim Design' int ernal procedure is
somewhat different . Aft er UniSim Design has convert ed each assay t o a
TBP vs. weight percent curve, all of t he individual curves are combined
t o produce a single composit e TBP curve. This composit e curve is t hen
used as if it were associat ed wit h a single assay; hypocomponent s are
generat ed based on your inst ruct ions.
These hypocomponent s are now common t o t he blended oil and all t he
const it uent oils. For each of t he const it uent oils, UniSim Design back
calculat es t he composit ions t hat correspond t o t hese hypocomponent s.
This procedure is recommended whenever recombining product oils or
fract ions t o produce a single inlet st ream, for example in generat ing a
feed for an FCCU main fract ionat or from analyzes of t he product
st reams. The maj or advant age t o blending is t hat fewer
hypocomponent s are used t o represent a given feed because duplicat e
Cut Opt i ons Descr i pt i on
Aut o Cut UniSim Design cut s t he assay based on int ernal values.
User Ranges You specify t he boiling point ranges and number of cut s per
range.
User Poi nt s You specify only how many hypocomponent you require.
UniSim Design proport ions t he cut s according t o an int ernal
weight ing scheme.
Caut i on shoul d be ex er ci sed w hen bl endi ng some
combi nat i ons of anal yzes. An i nher ent advant age, as w el l as
l i mi t at i on, of bl endi ng i s t hat al l const i t uent oi l s shar e a
common set of hy pocomponent and t her ef or e physi cal
pr oper t y char act er i st i cs. Any anal y zes t hat have l ar ge
over l appi ng TBP cur ves and ver y di f f er ent phy si cal pr oper t y
cur ves shoul d not be bl ended ( f or ex ampl e, hydr ocr ack er
r ecy cl es and f eedst ock s have si mi l ar TBPs but ver y di f f er ent
gr avi t y cur ves) . The phy si cal pr oper t i es of component s f or
over l appi ng ar eas r epr esent an aver age t hat may not
r epr esent ei t her of t he const i t uent assay s.
When you re- cut an oil,
UniSim Design will
aut omat ically updat e t he
associat ed flowsheet
st reams wit h t he new
hypocomponent s when
you leave t he Basis
Environment .
UniSim Design allows you
t o assign t he overall
blend composit ion and/ or
individual assay
composit ions t o st reams
via t he I nst all Oil t ab
( Sect i on 4. 8. 3 - I nst al l
Oi l Tab) .
4- 51
component s for overlapping TBP curves are eliminat ed.
A second advant age is t hat t he composit e TBP curve t ends t o smoot h
t he end port ions of t he individual assay curves where t hey may not be
as accurat e as t he middle port ions of t he curves.
Recommended Boiling Point Widt hs
The following t able is a guideline for det ermining t he number of split s
for each boiling point range. These are based upon t ypical refinery
operat ions and should provide sufficient accuracy for most applicat ions.
You may want t o increase t he number of split s for ranges where more
det ailed fract ionat ion is required.
Regardless of your input dat a, it is recommended t hat you limit your
upper boiling range t o 1650F ( 900C) . All of t he crit ical propert y
correlat ions are based on specific gravit y and normal boiling point s and
t hus, NBPs above t his limit may produce erroneous result s. The crit ical
pressure correlat ions cont rol t his limit . There is no loss in accuracy by
lumping t he heavy ends because increment al changes in solubilit y of
light er component s are negligible and t his range is generally not be
fract ionat ed.
Aut o Cut
I f you select t he Aut oCut opt ion, UniSim Design performs t he cut t ing
aut omat ically. UniSim Design uses t he boiling point widt h guidelines, as
shown previously:
User Point s
I f you select User Point s from t he Cut Opt ion Select ion drop- down list ,
Cut poi nt Range Boi l i ng Poi nt Wi dt h Cut s/ 100F
I BP t o 800F ( 425C) 25F ( 15C) per cut 4
800F t o 1200F ( 650C) 50F ( 30C) per cut 2
1200F t o 1650F ( 900C) 100F ( 55C) per cut 1
Range Cut s
100 - 800F 28
800 - 1200F 8
1200 - 1600F 4
4- 52
UniSim Design performs t he cut t ing process depending on t he number
of cut s you specify. Ent er t he t ot al number of cut s you want t o use for
t he oil in t he appropriat e field. All split s are based upon TBP
t emperat ure, independent of t he source or t ype of assay dat a. UniSim
Design proport ions t he cut s according t o t he following t able:
The int ernal weight ing produces more hypocomponent s per 100F
range at t he lower boiling point end of t he assay. For example, given a
TBP t emperat ure range of 100F t o 1400F and 38 component s
request ed, UniSim Design produces 28 component s for t he first range,
eight component s for t he second range and t wo component s for t he last
range:
( 800 - 100) / 100 * 4 = 28
( 1200 - 800) / 100 * 2 = 8
( 1400 - 1200) / 100 * 1 = 2
User Ranges
I f you want t o define cut point ranges and specify t he number of
hypocomponent in each range, select User Ranges and UniSim Design
displays t he Ranges Select ion informat ion as shown in t he figure below.
The I BP and FBP are shown above and t hese values corr espond t o t he
init ial boiling point and t he final boiling point of UniSim Design' int ernal
TBP working curve. At t his point all light ends are removed ( if
request ed) and t he I BP present ed is on a light ends free basis. Refer t o
t he Boiling Ranges Sect i on 4. 4 - Oi l Char act er i zat i on Vi ew for
definit ions of t he I BP and FBP.
Cut poi nt Range I nt er nal Wei ght i ng
I BP - 800F ( 425C) 4 per 100F
800F - 1200F ( 650C) 2 per 100F
1200F t o FBP 1 per 100F
Fi gur e 4. 34
4- 53
The I BP and FBP of t he int ernal TBP curve used for t he column
operat ion' s cut point specificat ions and t he boiling point t ables are
det ermined in t his manner. I f t he first or last hypocomponent has a
volume fract ion larger t han t hat defined by t he endpoint s for t he I BP or
FBP respect ively, t he TBP curve is ext rapolat ed using a spline fit .
You may supply t he st art ing Cut Point ; however, if t his field is left
blank, UniSim Design uses t he I BP. UniSim Design combines t he
mat erial boiling bet ween t he I BP and t he st art ing cut point t emperat ur e
wit h t he mat erial from t he first cut t o produce t he first component . This
component has an NBP cent roid appr oximat ely half way bet ween t hese
boundaries.
The next paramet ers t hat you must supply are t he upper cut point
t emperat ure and t he number of cut s for t he first cut point range. As
shown in Fi gur e 4. 34, t he upper cut point t emperat ure for t he first
range also corresponds t o t he lower boiling point of t he second cut point
range, so it does not have t o be re- ent ered. Aft er t he first cut range is
defined, only t he upper cut point t emperat ure and t he number of cut s
need t o be supplied for t he remaining ranges. I f t he final cut point
t emperat ure is not equal t o or great er t han t he FBP, UniSim Design
combines t he mat erial bet ween t he FBP and t he last cut t emperat ure
wit h t he mat erial in t he last component .
For example, assume t hat t he I BP and FBP are 40 and 1050F
respect ively, t he init ial cut t emperat ure is 100, t he upper limit for t he
first cut is 500 degrees, and t he number of cut s in t he first range is
eight .
Since t he boiling widt h for each component in t he first cut range is 50F
( i. e., [ 500- 100] / 8) , t he first component ' s NBP is at t he cent roid volume
of t he 40 t o 150 cut , in t his case approximat ely 95F. The remaining
component s have NBP values of appr oximat ely 175, 225, 275, 325,
375, 425 and 475F. The upper t emperat ure for t he second range is
1, 000 and t he number of cut s is equal t o 5. Since t he FBP is 1050, t he
mat erial in t he boiling range from 1, 000 t o 1, 050 is included wit h t he
last component .
4- 54
4. 6. 2 Correlat ions Tab
The Corr elat ions t ab of t he Blend propert y view is shown in t he figure
below:
The Corr elat ions t ab consist s of t he following obj ect s:
Fi gur e 4. 35
Sel ect ed
Cor r el at i on
Set
By default , t his is Default Set ( if you have changed t he
name of t he default set , t hat name is displayed) . You can
select anot her correlat ion set from t he Select ed drop- down
list , but first you must define one on t he Correlat ion t ab of
t he Oil Charact erizat ion propert y view.
You can define new correlat ions set s via t he Correlat ion
t ab, accessible from t he main Oil Charact erizat ion view.
See Sect i on 4. 8.1 - Cor r el at i on Tab.
Low and
Hi gh End
Temper at ur e
This is t he range for which t he Correlat ions are applied. I f
you split t he range, t hen more t han one t emperat ure range
is displayed.
You can edit t he t emperat ure of defined split s for cust om
Correlat ion Set s on t his t ab.
MW The MW correlat ion is displayed. You cannot change t he
correlat ion in t his view; t his can be done from t he
Correlat ion t ab accessible from t he main Oil
You can change only t he name of t he default set . I f you
want t o change any correlat ions, you must creat e a new
correlat ion set .
SG The specific gravit y ( densit y) correlat ion is displayed. You
cannot change t he correlat ion in t his view; t his can be done
from t he Correlat ion t ab accessible from t he main Oil
Tc, Pc, Acc.
Fact or , I deal
H
The crit ical t emperat ure, crit ical pressure, acent ricit y and
I deal Gas Ent halpy correlat ions are displayed. You cannot
change correlat ions on t his t ab; t his can be done in t he
Correlat ion view accessible from t he main Oil
Charact erizat ion view. To edit t he Select ed Correlat ion Set
from t his t ab, click t he Edit but t on. This t akes you t o t he
Correlat ion view.
As in t he Assay Oil
charact erizat ion, you
can only change t he
name of t he default set .
I f you want t o change
any correlat ions, you
must creat e a new
correlat ion set .
4- 55
The crit ical pressure, crit ical t emperat ure, acent ricit y and ideal gas
ent halpy correlat ions are required in t he Blend calculat ion ( or mor e
specifically, in t he calculat ion of hypocomponent propert ies) . I n t he
calculat ion of hypocomponent propert ies, t he molecular weight and
specific gravit y ( and viscosit y) are est imat ed from t heir respect ive
working curves.
4. 6. 3 Tables Tab
Aft er calculat ing a Blend, you can examine various propert y and flow
summaries for t he generat ed hypocomponent t hat represent a
calculat ed oil.
From t he Table Type drop- down list , you can select any one of t he
following:
Fi gur e 4. 36
Tabl e Ty pe Descr i pt i on
Component
Pr oper t i es
Wit h t his Table Type select ion, you can select one of t he t wo radio
but t ons in t he Table Cont rol group:
Mai n Pr oper t i es. Provides t he normal boiling point , molecular
weight , densit y and viscosit y informat ion for each individual
component in t he oil.
Ot her Pr oper t i es. Provides t he crit ical t emperat ure, crit ical
pressure, acent ric fact or, and Wat son K fact or for each
individual hypocomponent .
Component
Br eak dow n
Provides individual liquid volume%, cumulat ive liquid volume%,
volume flows, mass flows and mole flows, for t he input light ends
and each hypocomponent in t he oil.
Mol ar Composi t i ons Provides t he molar fract ion of each light end component and each
hypocomponent in t he oil.
4- 56
4. 6. 4 Propert y Plot Tab
UniSim Design can plot various propert ies versus liquid volume, mole or
mass percent dist illed. The x- axis choice is made from t he Basis drop-
down list . Any of t he following opt ions may be plot t ed on t he y- axis by
making a select ion from t he Propert y drop- down list :
Dist illat ion. A t able appears in which you can select which boiling
point curves t o examine. Act ivat e t he checkbox of each curve
you want displayed. The opt ions include: TBP, ASTM D86,
D86( Crack Reduced) , ASTM D1160( Vac) , ASTM D1160( At m) and
ASTM D2887.
Molecular Weight
Densit y
Viscosit ies at 100 and 210F ( or t he input t emperat ure)
Crit ical Temperat ure
Crit ical Pressure
Acent ric Fact or
User Propert y. A t able appears t o allow you t he choice of which
user propert y t o plot .
Click t he Clone and shelf t his plot but t on t o st ore t he current plot .
UniSim Design aut omat ically names t he plot wit h t he following format :
' t he name of t he act ive blend' - ' number of plot s creat ed' . For inst ance,
t he first plot creat ed for Blend- 1 would be named Blend- 1- 0, and any
subsequent plot s would have t he number aft er t he dash increment ally
increased.
Oi l Pr oper t i es For t his select ion, you can select t he Basis ( liquid volume, molar or
mass) in t he Table Cont rol group box. There are also t hree radio
but t ons, each producing a different t able:
Di st i l l at i on. Provides TBP, ASTM D86, D86 Crack Reduced,
ASTM D1160 ( Vac) , ASTM D1160 ( At m) , and ASTM D2887
t emperat ure ranges for t he oil.
Ot her Pr oper t i es. Provides crit ical t emperat ure, crit ical
pressure, acent ric fact or, molecular weight , densit y and
viscosit y ranges for t he oil.
User Pr oper t i es. Provides all user propert y ranges for t he oil.
Oi l Di st r i but i ons Provides t abular informat ion on how your assay would be roughly
dist ribut ed in a fract ionat ion column. Examine t he End Temperat ures
of t he various ranges as well as t he Cut Dist ribut ions. You can select
t he basis for t he Cut Dist ribut ion Fract ions ( Liquid Volume, Molar,
Mass) in t he Table Cont rol group. The radio but t ons provide t he
opt ion of st andard fract ionat ion cut s or user defined cut s:
St r ai ght Run. List s crude column cut s: Off gas, LSR Napht ha,
Napht ha, Kerosene, Light Diesel, Heavy Diesel, At mos Gas Oil
and Residue.
Cy cl e Oi l . List s Cat Cracker cycle oils: Off Gas, LC Napht ha, HC
Napht ha, LCGO, I CGO, HCGO, Residue 1 and Residue 2.
Vacuum Oi l . List s vacuum column cut s: Off Gas, LVGO, HVGO
and 5 VAC Residue ranges.
User Cust om. Allows for t he definit ion of cust omized
t emperat ure ranges. I f changes are made t o t he informat ion in
any of t he st andard fract ionat ion cut s, t he radio but t on will
aut omat ically swit ch t o User Cust om.
Tabl e Ty pe Descr i pt i on
Not e t hat in UniSim Design
t he following blend obj ect s
align wit h t he following
dist illat ion t emperat ure
curves:
D86CorrectedTemperature
Value = ASTM D86
D86TemperatureValue =
D86( Crack Reduced)
Refer t o t he Sect i on
4. 6. 7 - Pl ot Summar y
Tab sect ion for
informat ion concerning
t he Plot Summary t ab.
4- 57
To edit plot labels, you must clone t he plot using t he Clone and shelf
t his plot but t on. The BlendPlot appears and is st ored in t he Plot
Summary t ab.
An example of a TBP curve on a liquid volume basis for an oil is shown
below.
4. 6. 5 Dist ribut ion Plot Tab
UniSim Design can also plot a dist ribut ion bar chart so you can st udy
how your assay would be roughly dist ribut ed in a fract ionat ion column.
St raight Run, Cycle Oil, Vacuum Oil and User Cust om TBP cut point s are
available dist ribut ion opt ions, as shown by t he radio but t ons in t he Cut
I nput I nformat ion group. You can choose t he Basis for t he Cut
Dist ribut ion Fract ions ( Liquid Volume, Molar, Mass) in t he Plot Cont rol
Pl ot l abel s can not be modi f i ed w i t hi n t he Pr oper t y Pl ot t ab
Bl end vi ew .
Fi gur e 4. 37
4- 58
group.
Click t he Clone and shelf t his plot but t on t o st ore t he current plot .
t he name of t he act ive blend' - ' number of plot s creat ed' .
For example, t he first plot creat ed for Blend- 1 is named Blend- 1- 0, and
any subsequent plot s would have t he number aft er t he dash
increment ally increased. All st ored plot s are list ed on t he Plot Summar y
t ab.
To edit plot labels, you must clone t he plot using t he Clone and shelf
t his plot but t on. The BlendPlot appears and is st ored in t he Plot
Summary t ab.
I f changes are made t o t he names or end t emperat ures in any of t he
st andard fract ionat ion cut s, t he radio but t on aut omat ically swit ches t o
User Cust om.
Fi gur e 4. 38
Pl ot l abel s can not be modi f i ed w i t hi n t he Di st r i but i on t ab
Bl end vi ew .
4. 6. 7 - Pl ot Summar y
Tab for informat ion
concerning t he Plot
Summary t ab.
4- 59
An example dist ribut ion plot is shown in t he following figure.
4. 6. 6 Composit e Plot Tab
The Composit e Plot t ab allows you t o visually check t he mat ch bet ween
t he input assay dat a and t he calculat ed propert y curves. The choice for
t he graphical comparison is made from t he Pr oper t y drop- down list :
Dist illat ion
Molecular Weight
Densit y
Viscosit y
User Proper t y
Click t he Cl one and shel f t hi s pl ot but t on t o st ore t he current plot .
' t he name of t he act ive blend' - ' number of plot s creat ed' .
For example, t he first plot creat ed for Blend- 1 is named Blend- 1- 0, and
any subsequent plot s have t he number aft er t he dash increment ally
increased. All st ored plot s are list ed on t he Pl ot Summar y t ab.
To edit plot labels, you must clone t he plot using t he Cl one and shel f
t hi s pl ot but t on. The BlendPlot appears and is st ored in t he Pl ot
Summar y t ab.
An example molecular weight curve comparison is shown in t he
Fi gur e 4. 39
4. 6.7 - Pl ot Summar y
Tab for informat ion
concerning t he Plot
Summary t ab.
Plot labels can not be
modified wit hin t he
Composit e t ab Blend
view.
4- 60
following figure.
The calculat ed molecular weight lies above t he input curve ( inst ead of
over- laying it ) because t he calculat ed curve has been shift ed t o mat ch
an input bulk MW.
4. 6. 7 Plot Summary Tab
On t his t ab, you can view t he list of st ored plot s for t he current blend.
From t he Creat ed Plot s group you can access any st ored plot s or
remove plot s from t he list . The list of creat ed plot s are generat ed from
t he Propert y, Dist ribut ion, and Composit e Plot s t abs and shown below.
Access a plot by double- clicking on it s name or by obj ect inspect ing it s
name and select ing View from t he menu. From t he BlendPlot view, you
can edit plot labels by right - clicking and select ing t he graph cont rol
opt ion. This met hod of modifying plot s is pr eferable, since you can plot
what you want and t hat t here is a single locat ion for viewing t hem.
The cloned plot s are independent , t hus t he labels can be modified and
are not overwrit t en. The plot t ed dat a for t he cloned plot s is also
updat ed as t he blend changes.
Click t he Remov e but t on t o remove a select ed plot from t he list . Only
one plot can be removed from t he list at a t ime.
4. 6. 8 Not es Tab
Blend for your own fut ure reference.
Fi gur e 4. 40
There is no confirmat ion
message when you click
t he Remove but t on.
4- 61
4. 7 User Propert y
A User Propert y is any propert y t hat can be defined and subsequent ly
calculat ed on t he basis of composit ions. Examples for oils include
R. O. N. and Sulfur cont ent . During t he charact erizat ion process, all
hypocomponent s are assigned an appropriat e propert y value. UniSim
Design t hen calculat es t he value of t he propert y for any flowsheet
st ream. This enables User Propert ies t o be used as Column
specificat ions.
Aft er User Propert ies are inst alled, you can t hen supply assay
informat ion as for Viscosit y, Densit y or Molecular Weight Curves.
4. 7. 1 User Propert y Tab
The User Proper t y t ab of t he Oil Charact erizat ion propert y view is
shown below:
The Available User Proper t ies are list ed in t he left port ion of t he view.
The following User Propert y manipulat ion but t ons are available:
Fi gur e 4. 41
Vi ew Edit t he current ly highlight ed User Propert y.
Add Creat e a new User Propert y ( see t he following sect ion, User
Propert y View) .
Del et e Erase t he current ly highlight ed User Propert y. UniSim
Design does not prompt for confirmat ion when delet ing a
User Propert y.
Cl one Creat e a new User Propert y wit h t he same propert ies as t he
current ly highlight ed User Propert y. UniSim Design
immediat ely opens a new User Propert y view ( see t he
following sect ion, User Propert y View) .
User Cur v es Tab for an
explanat ion of at t aching
User Propert ies t o
exist ing Assays.
sect ion:
I nformat ion.
all Assay and Blend
informat ion.
The Oi l Out put
Set t i ngs. . . but t on
and ASTM D2887
int erconversion
4- 62 User Pr oper t y
4- 62
For a highlight ed User Propert y, you can edit t he name and provide a
descript ion.
4. 7. 2 User Propert y View
When you first open t his view, t he Name field has focus. The name of
t he User Propert y must be 12 charact ers or less.
Equat ion Paramet ers
The following opt ions are available for t he Basic user prop definit ion
Fi gur e 4. 42
User Pr oper t i es for
User Propert ies.
4- 63
group:
Par amet er Descr i pt i on
Mi x i ng Basi s You have t he following opt ions: Mole Fract ion, Mass
Fract ion, Liquid Volume Fract ion, Mole Flow, Mass Flow,
and Liquid Volume Flow.
All calculat ions are performed using composit ions in
UniSim Design int ernal unit s. I f you have specified a
flow basis ( molar, mass or liquid volume flow) , UniSim
Design uses t he composit ion as calculat ed in int ernal
unit s for t hat basis. For example, a User Propert y wit h
a Mixing Basis specified as molar flow is always
calculat ed using composit ions in kg mole/ s, regardless
of what t he current default unit s are.
The choice of Mixing Basis applies only t o t he basis
t hat is used for calculat ing t he propert y in a st ream.
You supply t he propert y curve informat ion on t he same
basis as t he Boiling Point Curve for your assay.
Mi x i ng Rul e Select from one of t hree mixing rules:
where:
P
mix
= t ot al user propert y value
P( i) = input propert y value for component
x( i) = component fract ion or flow, depending on
t he chosen Mixing Basis
f1, f2 = specified const ant s
Mi x i ng
Par amet er s
The mixing paramet ers f1 and f2 are 1. 00 by default .
You may supply any value for t hese paramet ers.
Uni t Ty pe This opt ion allows you t o select t he variable t ype for
t he user propert y. For example, if you have a
t emperat ure user propert y, select t emperat ure in t he
unit t ype using t he drop- down list .
Low er / Upper
Li mi t Val ue
This opt ion allows you t o define t he lower/ upper limit
values for t his user propert y.
User Pr oper t i es for
more det ail on t he Mixing
Rules.
P
mix
( )
f 1
f 2 x i ( )P i ( )
f 1
( )
i 1 =
N
=
P
mix
( )
f 1
f 2 x i ( ) P i ( ) ( )
f 1
ln ( )
i 1 =
N
=
f1 P
mix
- 10
f2 P
mix
-
+ x i ( ) f1 P i ( ) - 10
f2 P i ( ) -
+
\ .
| |
i 1 =
N
=
4- 64 Cor r el at i ons & I nst al l at i on
4- 64
Component User Propert y Values
I f you want , you may provide a Propert y value for all of t he Light End
component s you defined in t he Propert y Package. This is used when
calculat ing t he propert y value for each hypocomponent ( removing t hat
port ion of t he propert y curve at t ribut able t o t he Light Ends
component s) .
On t his view, you do not provide propert y curve informat ion. The
purpose of t his view is t o inst ruct UniSim Design how t he User Proper t y
should be calculat ed in all flowsheet st reams. Whenever t he value of a
User Propert y is request ed for a st ream, UniSim Design uses t he
composit ion in t he specified basis, and calculat e t he propert y value
using your mixing rule and paramet er s.
Not es Tab
User Proper t ies for your own fut ure refer ence.
4. 8 Correlat ions & I nst allat ion
4. 8. 1 Correlat ion Tab
UniSim Design allows you t o choose from a wide variet y of cor relat ions
t o det ermine t he propert ies of t he generat ed hypocomponent . From t he
Correlat ion t ab of t he Oil Charact erizat ion view, you can creat e
Once you have cal cul at ed a Bl end w hi ch i ncl udes an Assay
w i t h y our User Pr oper t y i nf or mat i on, t he val ue of t he User
Pr oper t y f or each hy pocomponent i s di spl ayed i n t he
Component User Pr oper t y Val ues gr oup.
Correlat ion set s can also
be viewed t hrough t he
Assay t ab -
Cor r el at i ons and Cut /
Bl end t ab -
Cor r el at i ons t ab.
4- 65
cust omized Correlat ion Set s.
The Available Corr elat ion Set s are list ed on t he left side of t he view. The
following Correlat ion manipulat ion but t ons are available:
For a highlight ed Correlat ion Set , you can edit t he name and provide a
descript ion.
Fi gur e 4. 43
But t ons Descr i pt i on
Vi ew Edit t he current ly highlight ed Correlat ion Set .
Add Creat e a new Correlat ion Set ( see t he following sect ion,
Correlat ion Set View) .
Del et e Erase t he current ly highlight ed Correlat ion Set . UniSim
Design does not prompt for confirmat ion when delet ing a
Correlat ion Set .
Cl one Creat e a new Correlat ion Set wit h t he same propert ies as
t he current ly highlight ed Correlat ion Set . UniSim Design
immediat ely opens a new Correlat ion Set view. Refer t o
Sect i on 4. 8.2 - Cor r el at i on Set Vi ew .
sect ion:
I nformat ion.
all Assay and Blend
informat ion.
The Oi l Out put
Set t i ngs. . . but t on
and ASTM D2887
int erconversion
4- 66
4. 8. 2 Correlat ion Set View
When you creat e or edit a Correlat ion Set , t he following view appears:
When you first open t his view, t he Name field has focus. The name of
t he Correlat ion Set must be 12 charact ers or less.
Correlat ions and Range Cont rol
Changes t o t he Molecular Weight or Specific Gravit y correlat ions are
applied t o t he curve ( Assay) , while t he cr it ical t emperat ure, crit ical
pressure, acent ric fact or and heat capacit y correlat ions apply t o t he
Blend' s hypocomponent propert ies. Changes t o t he Assay correlat ions
have no effect when you have supplied a propert y curve ( e. g.,
Molecular Weight ) ; t hey only apply in t he sit uat ion where UniSim
Design is est imat ing t he pr opert ies.
To change a correlat ion, posit ion t he cursor in t he appropriat e column
and select a new correlat ion from t he drop- down list .
The t able below shows t he UniSim Design default s and available opt ions
Fi gur e 4. 44
You cannot change t he cor r el at i ons or r ange f or t he Def aul t
Cor r el at i on Set . I f y ou w ant t o speci f y di f f er ent cor r el at i ons
or t emper at ur e r anges, y ou must cr eat e a new Cor r el at i on
Set .
The Working Curves
are calculat ed from
t he Assay dat a,
incorporat ing t he
Molecular Weight and
Specific Gravit y
correlat ions.
The
Hypocomponent s are
generat ed based on
your cut opt ion
select ions.
Finally, t he
hypocomponent
propert ies are
generat ed:
The NBP, molecular
weight , densit y and
viscosit y are
det ermined from t he
Working curves.
The remaining
propert ies are
calculat ed,
incorporat ing t he
crit ical t emperat ure,
crit ical pressure,
acent ric fact or and
heat capacit y
correlat ions.
4- 67
for t hese propert ies.
You have t he choice of changing a propert y correlat ion over t he ent ire
range, or making a cer t ain correlat ion valid for a part icular boiling point
range only. To split correlat ions over several boiling ranges click t he Add
Pr oper t y
Def aul t
Cor r el at i on
Opt i onal Cor r el at i ons
MW Twu Lee- Kesler
Aspen
Penn St at e
Kat z-
Firoozabadi
Hariu- Sage
API
Robinson- Peng
Whit son
Riazi- Daubert
Bergman
Kat z- Nokay
Modified
Kesler- Lee
Aspen least -
squares
Twu
Chung
Modified Twu
Pc Lee- Kesler Rowe
St anding
Lyderson
Penn St at e
Mat hur
Twu
Cavet t
Riazi- Daubert
Edmist er
Bergman
Aspen
Tc Lee- Kesler Rowe
St anding
Nokay
Penn St at e
Mat hur
Spencer-
Daubert
Chen- Hu
Meissner-
Redding
Cavet t
Riazi- Daubert
Edmist er
Bergman
Aspen
Roess
Eat on- Port er
Twu
SG Const ant Wat son
K
Bergman
Yarborough
Lee- Kesler
Bergman- PNA
Hariu- Sage
Kat z-
Firoozabadi
I deal H Lee- Kesler Cavet t
Modified Lee-
Kesler
Fallon- Wat son
Accent r i c
Fact or
Lee- Kesler Edmist er
Robinson Peng
Bergman
Twu
The Ri azi - Dauber t cor r el at i on has been modi f i ed by Whi t son.
The St andi ng cor r el at i on has been modi f i ed by Mat hew s-
Rol and- Kat z. The def aul t cor r el at i ons ar e t ypi cal l y t he best
f or nor mal hy dr ocar bon sy st ems. An upper l i mi t of 1250F
( 675C) i s suggest ed f or t he heav i est component . Al t hough
t he equat i ons have been modi f i ed t o ex t end beyond t hi s
r ange, some caut i on shoul d be ex er ci sed w hen usi ng t hem
f or ver y heavy sy st ems. Hi ghl y ar omat i c sy st ems may show
bet t er r esul t s w i t h t he Aspen cor r el at i ons.
Det ailed discussions
including t he range of
applicabilit y for t he
correlat ions is found in
Appendi x B - Oi l
Met hods &
Cor r el at i ons.
4- 68
New Range but t on and t he following view appears.
Ent er t he t emperat ure where you want t o make t he split int o t he New
Temp cell ( in t his case 400C) , and click t he Split Range but t on. The
t emperat ure is placed in t he cor relat ion set , and t he Correlat ion t able is
split as shown below:
You can now specify correlat ions in t hese t wo ranges.
You can add more split s.
You can also delet e a split ( merge range) by select ing t he
Remove Range but t on as shown in Fi gur e 4.46.
Highlight ing t he appropriat e t emperat ure in t he Temperat ure Range list
and select ing t he Merge Temp Range but t on removes or merges t he
t emperat ure range. When you merge a range, any corr elat ions you
Fi gur e 4. 45
Fi gur e 4. 46
When y ou mer ge a r ange, you del et e t he cor r el at i ons f or t he
r ange w hose Low End Temper at ur e i s equal t o t he r ange
t emper at ur e you ar e mer gi ng.
4- 69
chose for t hat range is forgot t en.

Assay & Blend Associat ion
The different component s of t he Assay and Blend Associat ion group are
described below:
Not es Tab
Corr elat ions for your own fut ure reference.
4. 8. 3 I nst all Oil Tab
The I nst all Oil t ab of t he Oil Charact erizat ion propert y view is shown
Any changes t o t he cor r el at i ons f or an I nput Assay r esul t s i n
f i r st t he assay bei ng r ecal cul at ed, f ol l ow ed by any bl end
w hi ch uses t hat assay. For an ex i st i ng oi l , i t w i l l be
aut omat i cal l y r ecal cul at ed/ r e- cut usi ng t he new
cor r el at i ons, and t he new component s ar e i nst al l ed i n t he
f l ow sheet .
New Assay s/ Bl ends I f you check t his, all new Assays and Blends t hat
are creat ed use t his Correlat ion Set .
Av ai l abl e Assay s/
Av ai l abl e Bl ends
These radio but t ons t oggle bet ween Assay or
Blend informat ion.
Assay / Bl end Tabl e This t able list s all Assays or Blends wit h t heir
associat ed Correlat ion Set s, depending on which
radio but t on is select ed. You can check t he Use
t his Set checkbox t o associat e t he current
Correlat ion Set wit h t hat Assay or Blend.
You can also select t he Correlat ion Set for a
specific Assay on t he Correlat ion t ab of t hat Assay
view.
4- 70
below:
You may inst all a calculat ed Blend int o your UniSim Design case; it
appears in t he Oil Name column of t he t able. Simply pr ovide a St ream
name for t hat Blend, and ensure t hat t he I nst all box is checked. You
may use an exist ing st ream name, or creat e a new one. I f you do not
provide a name or you deact ivat e t he I nst all box( es) , t he
hypocomponent is not at t ached t o t he fluid package. You can inst all an
oil t o a specific subflowsheet in your case by specifying t his in t he Flow
Sheet column.
Each inst alled Oil appears in t he component list as a series of
hypocomponent s named NBP[ 1] * * * , NBP[ 2] * * * , wit h t he 1
represent ing t he first oil inst alled, 2 t he second, et c. ; and * * * t he
average boiling point of t he individual Oil component s. UniSim Design
also assigns t he Light Ends composit ion, if present , in t he flowsheet
st ream.
When a Blend is inst alled in a st ream, t he relat ive flow rat e of each
const it uent Assay is defined wit hin t he Oil Charact erizat ion and cannot
be changed. However, if you inst all each of t he const it uent Assays
( represent ed by Blends wit h a single Assay) int o t heir own flowsheet
st ream, various combinat ions can be examined using Mixer or Mole
Balance operat ions. The flow and composit ion for each const it uent oil is
t ransferred t o your designat ed flowsheet st reams. The flow rat e of any
specified Oil st ream ( as opposed t o t he const it uent s of a Blend) can be
changed at any t ime by re- specifying t he st ream rat e in t he flowsheet
sect ion.
Fi gur e 4. 47
I f you want t o inst all t he
hypocomponent int o a
non-Associat ed Fluid
Package, Add t he Oil
Hypo group from t he
Component s t ab of t hat
Fluid Package view.
For Blends t hat cont ain
more t han one Assay -
each individual Assay is
aut omat ically displayed in
t he Oil I nst all I nformat ion
t able.
4- 71
4. 9 TBP Assay - Example
I n t his example, a crude oil wit h a TBP assay cur ve ext ending from
100F t o 1410F is charact erized. Associat ed wit h t his TBP assay are:
A dependent molecular weight curve
An independent API gravit y curve
Two independent viscosit y curves, one at 100F and t he ot her at
210F
The bulk molecular weight and bulk API gravit y
A liquid volume Light Ends assay for t he crude oil
I t is desired t o split t he assay int o 38 hypocomponent s, wit h 25F cut s
bet ween 100 and 800F, 50F cut s bet ween 800 and 1200F, and t he
remaining port ion of t he crude assay int o t wo component s.
The following assay informat ion is available:
Bul k Cr ude Pr oper t i es
MW 300
API Gr av i t y 48. 75
Li ght Ends Li qui d Vol ume%
Pr opane 0.0
i - But ane 0.19
n- But ane 0.11
i - Pent ane 0.37
n- Pent ane 0.46
TBP Di st i l l at i on Assay
Li qui d Vol ume% Temper at ur e ( F) Mol ecul ar Wei ght
0.0 80. 0 68.0
10. 0 255. 0 119. 0
20. 0 349. 0 150. 0
30. 0 430. 0 182. 0
40. 0 527. 0 225. 0
50. 0 635. 0 282. 0
60. 0 751. 0 350. 0
70. 0 915. 0 456. 0
80. 0 1095.0 585. 0
90. 0 1277.0 713. 0
98. 0 1410.0 838. 0
Dependent propert y
curves have values at
t he same dist illat ion
percent age as t he Boiling
Temperat ure assay, but
does not need t o have
values at every
percent age.
4- 72 TBP Assay - Ex ampl e
4- 72
4. 9. 1 I nit ializat ion
Before you can st art t he act ual charact erizat ion process, you must :
1. Begin a new UniSim Design case.
2. Select an appropriat e propert y package.
3. Add any non- oil component s, including t he Light Ends t hat are t o be
used in t he charact erizat ion pr ocess, t o t he component list .
I n t his case, use t he Peng- Robinson equat ion of st at e, and select t he
following component s: C3, i- C4, n- C4, i- C5, and n- C5. Aft er you have
select ed t he Light End component s, click t he Oil Environment icon on
t he t oolbar t o ent er t he Oil Charact erizat ion environment .
Prior t o t he input of assay dat a, a cust omized Unit Set is creat ed such
t hat t he default unit s used by UniSim Design correspond t o t he assay
dat a unit s. Creat e a cust omized unit set by cloning t he Field unit set .
Select API as t he new unit for bot h Mass Densit y and St andard Densit y
and leave all ot her Field default unit s as t hey are.
You can view a display of import ant messages relat ed t o t he progress of
t he charact erizat ion in t he Trace Window. I f you want , open t he Trace
Window at t he bot t om of t he Deskt op.
The main view in t he Oil Environment is t he Oil Charact erizat ion
API Gr avi t y Assay
Li q Vol % Di st i l l ed API Gr avi t y
13. 0 63. 28
33. 0 54. 86
57. 0 45. 91
74. 0 38. 21
91. 0 26. 01
Vi scosi t y Assay
Li q Vol % Di st i l l ed Vi sc. ( cP) 100F Vi sc. ( cP) 210F
10. 0 0.20 0.10
30. 0 0.75 0.30
50. 0 4.20 0.80
70. 0 39. 00 7.50
90. 0 600. 00 122. 30
Fl ui d Pack age for
det ails on inst alling a
fluid package.
Oil Environment icon
12. 3. 1 - Uni t s Page of
t he Uni Si m Desi gn User
Gui de for det ails on
creat ing a cust omized
unit set .
For more informat ion
concerning t he Trace
Window, refer t o Sect i on
1. 3 - Obj ect St at us
Wi ndow / Tr ace
Wi ndow of t he Uni Si m
4- 73
propert y view, as shown below:
The t abs are organized according t o t he general procedure followed in
t he charact erizat ion of an oil. Complet ing t he charact erizat ion requires
t hree st eps:
1. Access t he Assay view by select ing t he Add but t on on t he Assay
t ab of t he Oil Charact erizat ion view. I nput all of t he assay dat a on
t he I nput Dat a t ab of t he Assay view and click t he Cal cul at e
but t on.
2. Access t he Cut / Bl end view ( which also gives you cut t ing opt ions)
by select ing t he Add but t on on t he Cut / Bl end t ab of t he Oil
Charact erizat ion propert y view. Cut t he assay int o t he required
number of hypocomponent using t he cut point s out lined pr eviously.
3. I nst all t he calculat ed oil from t he Oil Environment int o t he flowsheet
by accessing t he I nst al l Oi l t ab of t he Oil Charact erizat ion propert y
view.
Alt hough you can access t he User Propert y t ab and t he Correlat ion t ab
from t he Oil Charact erizat ion view, neit her of t hese t abs are used in
t his example.
4. 9. 2 St ep 1 - I nput Assay Dat a
On t he Assay t ab of t he Oil Charact erizat ion view, select t he Add
but t on. This opens t he Assay view and places t he act ive locat ion in t he
Name cell of t he I nput Dat a t ab. For t his example, change t he name of
t he Assay t o Example. The Assay t ab is shown below.
The first t ime you ent er t his view, it is blank, except for t he Bulk
Fi gur e 4. 48
These t hree st eps are t he
minimum requirement s in
defining and inst alling an
oil.
4- 74
Propert ies field and t he Assay Dat a Type field.
Defining t he Assay
The I nput Dat a t ab is split int o t wo groups: Assay Definit ion and I nput
Dat a. As it s name implies, t he Assay Definit ion group is where t he
propert ies of t he assay are defined. Since bulk propert y dat a is
provided, select Used from t he Bulk Propert ies drop- down list . The bulk
propert ies appears in t he I nput Dat a group. Next from t he Assay Dat a
Type drop- down list , select TBP. The Bulk Props and Dist illat ion radio
but t ons are now visible.
Light ends can be Aut o Calculat ed by UniSim Design, however since you
are provided wit h t he light ends dat a, select I nput Composit ions from
t he Light Ends drop- down list .
Now, set t he Molecular Weight , Densit y and Viscosit y curve opt ions in
each of t he respect ive drop- down list s. The Molecular Weight curve is
Dependent , t he Densit y curve is I ndependent , and t he Viscosit y curves
are also I ndependent . As you specify t hese opt ions, radio but t ons
corresponding t o each curve are added t o t he I nput Dat a group box.
Now t hat t he Assay is sufficient ly defined, you can begin ent ering assay
dat a.
Specifying Assay Dat a
Specificat ion of t he Assay occurs in t he I nput Dat a group. The field and
opt ions visible inside t he group are dependent on which radio but t on is
select ed in t he I nput Dat a group.
Fi gur e 4. 49
The layout of t his view
depends on:
1. Which Dat a Type you
have select ed. This
mainly affect s what Dat a
Type opt ions are
available ( Dist illat ion,
Light Ends, et c. )
2. Which I nput Dat a
radio but t on you have
select ed. When you
specify t hat you have
I ndependent or
Dependent Molecular
Weight , Densit y or
Viscosit y dat a, a new
radio but t on is added t o
t he view. I n t his view,
t he TBP Dat a Type is
select ed and t he
Dist illat ion radio but t on
is select ed.
4- 75
UniSim Design calculat es int ernal working curves using t he supplied
propert y cur ve dat a. For each proper t y curve, you can select t he
met hod used for t he Ext rapolat ion of t he working cur ve. The
Ext rapolat ion met hod for each working cur ve is specified in t he Curve
Fit t ing Met hods group of t he Calculat ion Default s t ab.
Bulk Props
Select t he Bulk Props radio but t on. I nput a Bulk Molecular Weight ( 300)
and Bulk Mass Densit y ( 48. 75 API _60) as shown in t he figure below.
No bulk viscosit y informat ion is available, so leave t he Viscosit y cells
blank. I t is not necessary t o delet e t he Viscosit y Temperat ures as t hese
are ignored if you do not provide bulk viscosit ies.
Light Ends
Next , select t he Light Ends radio but t on. The I nput Dat a group displays
a Light Ends Basis drop- down list and a Light Ends Composit ion t able.
From t he dr opdown list , select LiquidVolume as t he Light Ends Basis
and ent er t he Light Ends composit ion as shown below:
Fi gur e 4. 50
Fi gur e 4. 51
4- 76
Dist illat ion
Select t he Dist illat ion radio but t on t o view t he TBP Dist illat ion assay. To
ent er t he dat a, click t he Edit Assay but t on. The Assay I nput Table view
appears and ent er t he following assay dat a:
Molecular Weight
Select t he Molecular Weight radio but t on t o view t he Molecular Weight
dat a. You need only ent er t he Molecular Weight s as shown below:
Densit y
Select t he Densit y radio but t on t o view ( or edit ) t he Densit y assay. The
default densit y unit s are displayed, in t his case API . The complet ed API
Fi gur e 4. 52
Fi gur e 4. 53
As you ent er values int o
t he t able, t he cursor
aut omat ically moves down
aft er each ent ry, making it
easier t o supply all values
in each column.
Since t he Molecular
Weight assay is
Dependent , t he Assay
Percent age values t hat
you ent ered for t he Boiling
Point Temperat ure assay
are aut omat ically
displayed.
4- 77
gravit y curve input is shown below:
Viscosit y
Select t he Viscosit y1 and Viscosit y2 radio but t ons t o view ( or edit ) t he
Viscosit y assays. When eit her of t hese but t ons ar e select ed, an
addit ional input box is displayed, which allows you t o supply t he
viscosit y t emperat ures. Make sure t he Use Bot h radio but t on is select ed
in t he Viscosit y Curves group box. The required viscosit y input is shown
below:
Calculat ing t he Assay
Aft er ent ering all of t he dat a, go t o t he Calculat ion Default s t ab. The
Fi gur e 4. 54
Fi gur e 4. 55
Ensure t hat t he Viscosit y
Unit s Type is Dynamic,
and t hat t he t wo
t emperat ures ent ered are
100F and 210F.
4- 78
ext rapolat ion met hods displayed in t he Curve Fit t ing Met hods gr oup.
The default ext rapolat ion met hods for t he working curves are adequat e
for t his assay. To begin t he calculat ion of t he assay, pr ess t he Calculat e
but t on. The st at us message at t he bot t om of t he Assay view shows t he
message Assay Was Calculat ed.
Aft er t he Assay is calculat ed, t he working curves are displayed on t he
Working Curves t ab.
The working curves for t he normal boiling point , molecular weight ,
mass densit y and viscosit y are regressed fr om your input curves.
UniSim Design uses 50 point s in t he calculat ion of t he working curves,
Fi gur e 4. 56
Fi gur e 4. 57
Char act er i zi ng Assay s
for informat ion on t he
charact erizat ion
procedure, working curves
and ext rapolat ion
met hods.
4- 79
but t he molar dist ribut ion varies depending on t he dat a you provide.
UniSim Design moves more point s t o a region wit h a st eep gradient .
The calculat ion of t he Blend is based on t hese working curves.
You can examine graphical repr esent at ions of your assay dat a on t he
Plot s t ab. Open t he Propert y drop- down list and select t he curve t hat
you would like t o view. The default plot is t he Boiling Point Temperat ure
( Dist illat ion) cur ve. Because input dat a for t he boiling t emperat ure,
molecular weight , densit y and viscosit y were provided, all of t hese
opt ions are shown in t he dr opdown list .
4. 9. 3 St ep 2 - Cut Assay int o
Hypocomponent s
You can now cut t he Assay int o individual hypocomponent s. On t he Cut /
Blend t ab of t he Oil Charact erizat ion view, select t he Add but t on. This
Fi gur e 4. 58
The opt ions available in
t he Propert y drop- down
list correspond t o t he
propert y curve dat a
specified on t he I nput
Dat a t ab. I f only bulk dat a
is provided, t here are no
plot s available.
I f mult iple assays are
blended, repeat t he st eps
out lined in Sect i on 4. 9. 2
- St ep 1 - I nput Assay
Dat a.
I f you have only one
Assay, it is not necessary
t o ent er a Flow Rat e in
t he Oil Flow I nformat ion
t able.
4- 80
t akes you t o t he Blend propert y view wit h t he list of available assays.
From t he Available Assays group, select Example and click t he Add
but t on. This adds t he Assay t o t he Oil Flow I nformat ion t able, and a
Blend ( Cut ) is aut omat ically calculat ed.
The Blend is calculat ed because t he default Cut Opt ion, Aut o Cut ,
appears as soon as a Blend is added. Since t he Cut Opt ion was not
changed prior t o t he addit ion of t he Available Assay t o t he Blend,
UniSim Design realizes enough informat ion is available t o cut t he oil
and t he calculat ions occur aut omat ically.
I nst ead of using t he default Cut Opt ion, t he cut point s are defined.
From t he Cut Opt ion drop- down list , select User Ranges. Ent er a
St art ing Cut Point Temperat ure of 100F and fill out t he Cut Point t able
Fi gur e 4. 59
Fi gur e 4. 60
4- 81
as shown on t he left . Click t he Submit but t on t o calculat e t he Blend.
The result s of t he calculat ion can be viewed on t he Tables t ab of t he
Blend view. The default Table Type is t he Component Propert ies t able
wit h t he Main Propert ies radio but t on select ed in t he Table Cont rol
group.
From t he dr opdown list , you can also view a Component Breakdown,
Molar Composit ions, Oil Propert ies, and Oil Dist ribut ions.
All of t he dat a t hat is found on t he Tables t ab can be viewed graphically
from t he following t hr ee t abs:
Propert y Plot
Dist r ibut ion Plot
Composit e Plot
On t he Dist ribut ion Plot t ab, select Liquid Volume fract ion from t he
Fi gur e 4. 61
Fi gur e 4. 62
Tabl es Tab for det ails
on t he informat ion
available on t he Tables
t ab.
4- 82
Basis drop- down list . The following plot is displayed:
The Cut Dist ribut ion Plot , as shown above, displays t he volume fract ion
of t he oil t hat would be recovered in various pr oduct s. This graph is
part icularly useful in providing est imat es for dist illat ion product s.
4. 9. 4 St ep 3 - Transfer
I nformat ion t o Flowsheet
The final st ep of t he charact erizat ion is t o t ransfer t he hypocomponent
informat ion int o t he flowsheet .
On t he I nst all Oil t ab of t he Oil Charact erizat ion view, ent er t he St ream
Name Example Oil, t o which t he oil composit ion is being t ransferred.
UniSim Design assigns t he composit ion of your calculat ed Oil and Light
Fi gur e 4. 63
Fi gur e 4. 64
Refer t o t he t ab
subsect ions in Chapt er
4. 6 - Hypocomponent
Gener at i on for
available plot s.
4- 83
Ends int o t his st ream, complet ing t he charact erizat ion procedure. Also,
t he hypocomponent is placed int o a Hypo group named Blend1 and
inst alled in t he fluid package. When you leave t he Oil Charact erizat ion
environment , you are placed in t he Basis envir onment . I t is here t hat
you can examine individual hypot het ical component s t hat makeup
your oil.
Ent er t he Simulat ion Environment and move t o t he Workbook t o view
t he st ream you j ust cr eat ed. The Composit ions page displaying t he
st ream Example Oil is shown below.
I f you decide t hat some of t he hypocomponent paramet ers need t o be
recalculat ed, you can ret urn t o t he Oil Environment at any t ime t o
make changes. To edit an Assay, highlight it on t he Assay t ab of t he Oil
Charact erizat ion propert y view, and click t he Edit but t on. I f you want t o
see t he effect of using a different correlat ions on your oil, you can
access t his informat ion on t he Cor relat ion t ab of t he Oil
Charact erizat ion view.
4. 9. 5 Fluid Package Associat ion
I n t he example shown in Fi gur e 4. 66, t here is only one fluid package
for t he flowsheet . Specifying t he st ream name ( Example Oil) not only
creat es t he st ream in t he flowsheet , but adds t he Hypo group ( which
Fi gur e 4. 65
4- 84 Sul f ur Cur v e - Ex ampl e
4- 84
cont ains all of t he individual hypocomponent s) t o t he fluid package.
When t here are mult iple fluid packages in t he simulat ion, you can
specify t he one wit h which t he Oil is t o be associat ed ( accessed t hrough
t he Oil Manager t ab of t he Simulat ion Basis Manager view) . This serves
t wo funct ions: first , it ident ifies which pure component s are available
for a light ends analysis, and second, it ident ifies t he fluid package t o
which t he Hypo group is being inst alled.
4. 10 Sulfur Curve - Example
The User Propert y opt ion in t he Oil Charact erizat ion environment allows
you t o supply a propert y curve and have UniSim Design charact erize it
wit h an Assay. Each hypocomponent is assigned a pr opert y value when
t he Blend is charact erized. You can specify t he basis upon which t he
propert y should be calculat ed ( mole, mass or liquid volume, and flows
or fract ions) , as well as which mixing rule should be used.
I n t his example, a TBP curve wit h an associat ed Sulfur Curve is
inst alled. There is no Light Ends analysis available, so t he Aut o
Calculat e Light Ends opt ion is used.
4. 10. 1 Fluid Package
Prior t o ent ering t he Oil Charact erizat ion environment , creat e a Fluid
Package wit h Peng- Robinson as t he propert y met hod and C1, C2, C3, i-
C4, and n- C4 as t he component s. The choice of t he Light Ends
component s is influenced by t he Sulfur Cur ve dat a ( r efer t o Sect i on
4. 10. 3 - I nst al l t he Assay sect ion) .
Fi gur e 4. 66
I n t his case, t he Oil is Associat ed wit h Fluid Package Basis- 1
4- 85
4. 10. 2 I nst all a User Propert y
Ent er t he Oil Environment by clicking t he Oil Environment icon on t he
t oolbar. To supply a User Curve for an assay, you must fir st add a User
Propert y. On t he User Propert y t ab of t he Oil Charact erizat ion view,
select Add t o access t he User Propert y view as shown below.
The default opt ions are used for t he Equat ion Paramet ers except for t he
Mixing Basis field. Sulfur is quot ed on a w/ w basis so, select Mass
Fract ion from t he drop- down list . UniSim Design aut omat ically names
and numbers t he User Propert ies. You can provide a descript ive Name
for t he propert y, such as Sulfur.
UniSim Design gives you t he opt ion of providing a Component User
Propert y Value for each Light End component . I f, for example, t his was
a Heat ing Value Propert y, you would supply each component value at
t his point . Since t hese component s do not have a Sulfur value" , 0 is
t he correct value t o be ent ered.
Fi gur e 4. 67
You can al so add a User Pr oper t y vi a t he User Pr oper t y t ab i n
t he Si mul at i on Basi s Manager .
Oil Environment icon
4- 86
4. 10. 3 I nst all t he Assay
Creat e an Assay by clicking t he Add but t on on t he Assay t ab of t he Oil
Charact erizat ion view. Select TBP as t he Assay Dat a Type, specify a
Liquid Volume% as t he Assay Basis, and leave t he TBP Dist illat ion
Condit ions group at t he default set t ings.
Since no Light Ends analysis is provided, select t he Aut o Calculat e from
t he Light Ends drop- down list . The Aut o Calculat e procedure replaces
t he port ion of t he TBP curve which is covered by t he Boiling Point range
of t he Light Ends component s. I n t his way, t he init ial boiling point of t he
TBP working curve is slight ly higher t han t he normal boiling point of t he
heaviest Light End component .
The TBP curve st art s at - 25C. Taking t his informat ion int o account ,
Light End component s wit h boiling point s t hat lie wit hin t he first t wo
percent of t he TBP assay were chosen. I n t his way, t he benefit s of t he
Aut o Calculat e procedure are gained wit hout losing a significant port ion
of our pr opert y curve.
There is no Molecular Weight , Densit y, or Viscosit y dat a, so you can
leave t he curve opt ions as Not Used. On t he Calculat ion Default s t ab,
t he ext rapolat ion met hod for t he Dist illat ion curve can be left at it s
default , Probabilit y. There are no bulk propert ies for t he assay. Provide
t he boiling t emperat ure dat a, as t abulat ed below:
TBP Dat a
Assay % Temp ( C) Assay % Temp ( C) Assay % Temp ( C)
0.02 - 25 20. 73 180 71.43 500
0.03 - 20 24. 06 200 73.86 520
0.05 - 10 27. 55 220 76.22 540
0.31 0 30. 93 240 78.46 560
0.52 10 34. 32 260 80.57 580
0.55 20 37. 83 280 82.55 600
1.25 30 41. 21 300 84.41 620
2.53 40 44. 51 320 86.16 640
2.93 50 48. 01 340 87.79 660
3.78 60 51. 33 360 89.32 680
4.69 70 54. 58 380 90.67 700
5.67 80 57. 73 400 93.48 750
7.94 100 60. 65 420 95.74 800
10. 69 120 63. 39 440 98.78 900
13. 84 140 66. 16 460
17. 28 160 68. 90 480
4- 87
The Assay view wit h t he TBP Dat a is shown below:
Sulfur Curve
On t he User Curves t ab of t he Assay propert y view, select t he Available
User Propert y Sulfur and click t he Add but t on. I n t he User Curve Dat a
group, select I ndependent as t he Table Type and ensure t hat t he Bulk
Value cell displays < empt y> . Click t he Edit but t on and ent er t he Sulfur
Curve Dat a shown below in t he Assay I nput Table.
Aft er t his dat a is ent ered, click t he Calculat e but t on found at t he
bot t om of t he Assay propert y view.
Fi gur e 4. 68
Sul f ur Cur v e Dat a
Assay % Sul f ur Val ue Assay % Sul f ur Val ue
0.90 0.032 54. 08 2.733
7.38 0.026 55. 85 2.691
11. 48 0.020 57. 17 2.669
16. 42 0.083 60. 00 2.670
22. 40 0.094 64. 47 2.806
26. 68 0.212 68. 40 3.085
31. 78 0.616 72. 09 3.481
36. 95 1.122 75. 66 3.912
42. 04 1.693 78. 99 4.300
47. 14 2.354 82. 05 4.656
48. 84 2.629 84. 85 4.984
50. 52 2.786 87. 38 5.286
52. 22 2.796 90. 33 5.646
4- 88
4. 10. 4 Creat e t he Blend
A Blend is cr eat ed using t he Aut o Cut opt ion. On t he Cut \ Blend t ab of
t he Oil Charact erizat ion view, select t he Add but t on. On t he Dat a t ab of
t he Blend view, highlight Assay- 1 from t he list of Available Assays and
click t he Add but t on. The assay is now added t o t he Oil Flow
I nformat ion t able. The Blend is immediat ely calculat ed, as t he default
Cut Opt ion is Aut o Cut .
4. 10. 5 Result s
Finally, t he user propert y is defined and needs t o be inst alled. On t he
I nst all Oil t ab of t he Oil Charact erizat ion view, specify t he St ream Name
Fi gur e 4. 69
4- 89
as Example Oil t o which t he oil composit ion is t ransferred.
UniSim Design assigns t he composit ion of your calculat ed Oil and Light
Ends int o t his st ream, complet ing t he charact erizat ion pr ocedure for
t he User Proper t y.
You can ret urn t o t he User Propert y t ab of t he Oil Charact erizat ion view
and click t he View but t on t o display t he Sulfur User Propert y view.
Fi gur e 4. 70
Fi gur e 4. 71
4- 90 Ref er ences
4- 90
I n t he Component User Proper t y Values group, t he Propert y Value is
calculat ed for all t he hypocomponent s for t he blend. You can scroll
t hrough t he t able t o view t he Propert y Value for each hypocomponent .
From t he Composit e Plot t ab of t he Blend view, you can view a plot of
t he Calculat ed and I nput t ed values for t he User Propert y. Select User
Propert y from t he Propert y dr opdown list and act ivat e t he Sulfur
checkbox t o view t he following figure.
4. 11 References
1
Figure 3A1. 1, Chapt er 3, API Technical Dat a Book, Fourt h Edit ion ( 1980) .
2
Procedure 3A1.1, Chapt er 3, API Technical Dat a Book, Fift h Edit ion ( 1987) .
3
Procedure 3A1.1, Chapt er 3, API Technical Dat a Book, Sixt h Edit ion ( 1994) .
4
Edmist er, W. C., and Okamot o, K. K., Applied Hydrocarbon Thermodynamics,
Part 12: Equilibrium Flash Vaporizat ion Correlat ions for Pet roleum
Fract ions, Pet roleum Refiner, August , 1959, p. 117.
5
Procedure 3A3.1, Chapt er 3, API Technical Dat a Book, Fift h Edit ion ( 1987) .
6
7
Fi gur e 4. 72
React i ons 5- 1
5- 1
5 React ions
5.1 I nt r oduct i on ............. ........................................................... .......... 2
5.2 React i on Component Sel ect i on ............................................ .......... 2
5.2.1 Adding Component s from Basis Manager ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 3
5.2.2 Select ions Wit hin t he React ion Manager . ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
5.2.3 Library React ion Component s . .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 5
5.3 React i ons .................. ........................................................... .......... 5
5.3.1 Manipulat ing React ions ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
5.3.2 Conversion React ion .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 7
5.3.3 Equilibrium React ion.. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 10
5.3.4 Kinet ic React ion . .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 16
5.3.5 Het erogeneous Cat alyt ic React ion. .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 21
5.3.6 Simple Rat e React ion. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 26
5.4 React i on Set s ............ ........................................................... .........29
5.4.1 Manipulat ing React ion Set s... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 30
5.4.2 React ion Set View ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 30
5.4.3 Export ing/ I mport ing a React ion Set ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 36
5.4.4 Adding a React ion Set t o a Fluid Package .. .. ... .. ... .. .. ... .. ... .. .. ... .. .. 37
5.4.5 React ions in t he Build Environment . ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 37
5.5 Gener al i zed Pr ocedur e......................................................... .........38
5.6 React i ons - Ex ampl e . ........................................................... .........39
5.6.1 Add Component s t o t he React ion Manager . .. ... .. ... .. .. ... .. ... .. .. ... .. .. 39
5.6.2 Creat e a React ion. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 39
5.6.3 Add t he React ion t o a React ion Set . ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 40
5.6.4 At t ach t he React ion Set t o a Fluid Package .. ... .. ... .. .. ... .. ... .. .. ... .. .. 41
5- 2
React ions wit hin UniSim Design are defined inside t he React ion
Manager. The React ion Manager, which is locat ed on t he React ions t ab
of t he Simulat ion Basis Manager, provides a locat ion from which you
can define an unlimit ed number of react ions and at t ach combinat ions of
t hese react ions in React ion Set s. The React ion Set s ar e t hen at t ached
t o Unit Operat ions in t he Flowsheet .
The React ion Manager is a ver sat ile, t ime- saving feat ure t hat allows
you t o do t he following:
Creat e a new list of component s for t he React ions or simply use
t he fluid package component s.
Add, Edit , Copy, or Delet e React ions and React ion Set s.
At t ach React ions t o various React ion Set s or at t ach React ion
Set s t o mult iple Fluid Packages, t hus eliminat ing repet it ive
procedures.
I mport and Export React ion Set s.
5. 2 React ion Component
Select ion
On t he React ions t ab of t he Simulat ion Basis Manager, t here are t hree
Fi gur e 5. 1
React i ons 5- 3
5- 3
main groups which are described below:
Each of t he main groups wit hin t he React ion Manager are examined in
more det ail. I n t his sect ion, t he Rxn Component s group is described.
The feat ures in t he React ions group and React ion Set s group are
det ailed in subsequent sect ions.
There are t hree dist inct ways in which component s can be made
accessible t o React ions in t he React ion Manager:
You can add component s on t he Component t ab of t he
Simulat ion Basis Manager. The component s are added t o t he
component list and are available in t he Rxn Component s group
t o be at t ached t o t he React ion Set . These component s are also
included in t he fluid package depending on t he component list
select ed for t he package.
You can inst all component s direct ly in t he React ion Manager
wit hout adding t hem t o a specific component list by clicking t he
Add Comps but t on. The Component List view appears and you
can add react ion component s for t he react ion. These
component s appear aut omat ically in t he mast er component list ,
but not in t he component list select ed for t he fluid package.
When a React ion Set ( cont aining a React ion which uses t he new
component s) is at t ached t o a fluid package, t he component s
which are not present in t he fluid package are aut omat ically
t ransferred.
You can select an Equilibrium React ion from t he Library t ab of
t he Equilibrium React or propert y view. All component s used in
t he r eact ion are aut omat ically inst alled in t he React ion Manager.
Once t he React ion Set ( cont aining t he Library react ion) is
at t ached t o a fluid package, t he component s are aut omat ically
t ransferred t o t he fluid package.
5. 2. 1 Adding Component s from
Basis Manager
Wit h t his met hod of component select ion, component s are select ed on
t he Component s t ab from t he Simulat ion Basis Manager. Add a
component list by clicking t he Add but t on. Fr om t he Component List
View, select t he component s which are required for t he react ion. This is
similar t o adding component s t o a component list for a part icular fluid
Gr oup Descr i pt i on
Rx n
Component s
Displays all component s available t o t he React ion Manager
and t he Add Comps but t on.
React i ons Displays a list of t he defined react ions and four but t ons
available t o help define react ions.
React i on
Set s
Displays t he defined react ions set s, t he associat ed fluid
packages and several but t ons t hat help t o define react ion
set s and at t ach t hem t o fluid packages.
Component s for more
informat ion on adding
component s.
React i on Set s for det ails
on at t aching a fluid
package.
Hypocomponent s creat ed
using t he Oil Manager can
be used in React ions.
They are list ed as
Associat ed Component s if
t hey are inst alled in a
fluid package. See
Chapt er 4 - Uni Si m
Desi gn Oi l Manager for
det ails on
hypocomponent .
5- 4 React i on Component Sel ect i on
5- 4
package or case. All component s t hat are select ed are displayed and
available in t he Rxn Component s gr oup of t he React ion Manager.
5. 2. 2 Select ions Wit hin t he
React ion Manager
Component s can be made available prior t o t he creat ion of React ions by
direct ly select ing t hem wit hin t he React ion Manager. By select ing t he
component s wit hin t he React ion Manager, you are not required t o
t ransfer component informat ion from t he fluid package. The
component s appear in t he Mast er Component list , but not in t he
component list . Once a React ion Set is at t ached t o a fluid package,
UniSim Design aut omat ically t ransfers all of t he component s cont ained
wit hin t he React ion( s) t o t he fluid package.
The following procedure demonst rat es t he st eps required when
beginning wit h a new case:
1. Creat e a new case by clicking t he New Case icon on t he t oolbar.
2. On t he Fluid Pkgs t ab of t he Simulat ion Basis Manager, click t he Add
but t on. A new fluid package is creat ed and it s propert y view opens.
Close t he Fluid Package proper t y view.
3. Move t o t he React i ons t ab. Click t he Add Comps but t on in t he Rxn
Component s group and t he Component List view is displayed.
4. Select eit her t radit ional or hypot het ical component s. The procedure
for select ing component s is similar t o t he select ion of component s
for t he fluid package.
5. Ret urn t o t he React ion Manager t o creat e t he React ion( s) and inst all
t he React ion( s) wit hin a React ion Set .
See Sect i on 5. 3 - React i ons, and Sect i on 5. 4 - React i on Set s
for det ails.
6. At t ach t he React ion Set t o t he fluid package cr eat ed in St ep # 2.
See Sect i on 5. 4. 4 - Addi ng a React i on Set t o a Fl ui d Pack age
for det ails.
7. All component s used in t he React ion( s) t hat are cont ained wit hin t he
React ion Set are now available in t he fluid package.
The component s l i st ed i n t he Sel ect ed React i on Component s
gr oup ar e avai l abl e t o any React i on t hat y ou cr eat e.
At least one fluid package
must exist before
component s can be
t ransferred from t he
React ion Manager.
New Case icon
React i ons 5- 5
5- 5
5. 2. 3 Library React ion
Component s
When a Library Equilibrium React ion is select ed, all of it s const it uent
component s are aut omat ically added t o t he React ion Manager. You can
t hen use t he component s in t he Rxn Component s group of t he React ion
Manager t o define ot her react ions. Library react ions can be inst alled
prior t o t he addit ion of component s t o t he case. You are not required t o
add component s using t he Component List view or React ion Manager.
To add a Library react ion, do t he following:
1. From t he React ion Manager, click t he Add Rx n but t on in t he
React ions group.
2. Highlight Equi l i br i um from t he React ions view and click t he Add
React i on but t on.
3. Move t o t he Li br ar y t ab of t he Equilibrium React ion propert y view
and select a react ion from t he Library Equilibrium Rxns group.
4. Click t he Add Li br ar y Rx n but t on. All library informat ion
concerning t he r eact ion is t ransf err ed t o t he various t abs of t he
Equilibrium React ion propert y view. The component s used by t he
react ion are now shown in t he Rxn Component s group of t he
React ion Manager.
5. 3 React ions
I n UniSim Design, a default react ion set , t he Global Rxn Set , is present
in every simulat ion. All compat ible react ions t hat are added t o t he case
are aut omat ically included in t his set . A React ion can be at t ached t o a
different set , but it also remains in t he Global Rxn Set unless you
Fi gur e 5. 2
React i on Set s for
informat ion on React ion
Set s.
5- 6 React i ons
5- 6
remove it . To creat e a React ion, click t he Add Rxn but t on from t he
React ion Manager.
The following t able describes t he five t ypes of React ions t hat can be
modeled in UniSim Design:
Each of t he react ion t ypes requir e t hat you supply t he st oichiomet ry. To
assist wit h t his t ask, t he Balance Error t racks t he molecular weight and
supplied st oichiomet ry. I f t he react ion equat ion is balanced, t his error is
equal t o zero. I f you have provided all of t he st oichiomet ric coefficient s
except one, you may select t he Balance but t on t o have UniSim Design
det ermine t he missing st oichiomet ric coefficient .
React ions can be on a phase specific basis. The React ion is applied only
t o t he component s present in t hat phase. This allows different rat e
equat ions for t he vapour and liquid phase in same react or operat ion.
React i on Ty pe Requi r ement s
Conver si on Requires t he st oichiomet ry of all t he component s in t he
react ion and t he conversion of a base component in
t he react ion.
Equi l i br i um Requires t he st oichiomet ry of all t he react ions. The
t erm Ln( K) may be calculat ed using one of several
different met hods, as explained lat er. The react ion
order for each component is det ermined from t he
st oichiomet ric coefficient s.
Het er ogeneous
Cat al y t i c
Requires t he st oichiomet ry of all t he component s in t he
react ion and t he paramet ers of t he react ion kinet ics
including t he surface react ion kinet ic paramet ers in t he
numerat or t erm and t he adsorpt ion kinet ic paramet ers
in t he denominat or t erm.
Ki net i c Requires t he st oichiomet ry of all t he component s in t he
react ion, as well as t he Act ivat ion Energy and
Frequency Fact or in t he Arrhenius equat ion for forward
and reverse ( opt ional) react ions. The forward and
reverse orders of react ion for each component can be
specified.
Si mpl e Rat e Requires t he st oichiomet ry of all t he component s in t he
react ion, as well as t he Act ivat ion Energy and
Frequency Fact or in t he Arrhenius equat ion for t he
forward react ion. The Equilibrium Expression const ant s
are required for t he reverse react ion.
React i ons 5- 7
5- 7
5. 3. 1 Manipulat ing React ions
From t he React ion Manager, you can use t he four but t ons in t he
React ions group t o manipulat e react ions. The but t ons are described
below:
5. 3. 2 Conversion React ion
The Conver sion React ion requires t he St oichiomet ric Coefficient s for
each component and t he specified Conversion of a base react ant . The
unknown composit ions of st reams can be calculat ed when t he
Conver sion is known.
Consider t he following Conver sion react ion:
where:
a, b, c, d = t he respect ive st oichiomet ric coefficient s of t he react ant s
( A and B) and product s ( C and D)
A = t he base react ant
I n general, t he react ion component s obey t he following react ion
st oichiomet ry:
But t on Command
Vi ew Rx n Accesses t he propert y view of t he highlight ed react ion.
Add Rx n Accesses t he React i ons view, from which you select a
React ion t ype.
Del et e Rx n Removes t he highlight ed react ion( s) from t he React ion
Manager.
Copy Rx n When select ed, t he Copy React ions view appears where you
can select an alt ernat e React ion Type for t he react ion or
duplicat e t he highlight ed react ion.
( 5. 1)
( 5. 2)
When you right - click a
react ion in t he React ions
group, you can select
View or Delet e from t he
Obj ect I nspect menu.
By default , conversion
react ions are calculat ed
simult aneously. However
you can specify sequent ial
react ions using t he
Ranking feat ure. See
Sect i on 5. 4 - React i on
Set s.
A
b
a
-- B
c
a
-- C
d
a
-- D + +
N
A
N
A
o
1 X
A
( ) =
N
B
N
B
o
b
a
-- N
A
o
X
A
=
N
C
N
C
o
c
a
-- N
A
o
X
A
( ) + =
N
D
N
D
o
d
a
-- N
A
o
X
A
( ) + =
5- 8 React i ons
5- 8
where:
N
*
= t he final moles of component * ( * = A, B, C and D)
N
* o
= t he init ial moles of component *
X
A
= t he conversion of t he base component A
The moles of a react ant available for conversion in a given react ion
include any amount produced by ot her react ions, as well as t he amount
of t hat component in t he inlet st r eam( s) . An except ion t o t his occurs
when t he react ions are specified as sequent ial.
St oichiomet ry Tab
The St oichiomet ry t ab of a conversion react ion is shown in t he figure
below:
For each Conver sion react ion, you must supply t he following
informat ion:
Fi gur e 5. 3
I nput Fi el d I nf or mat i on Requi r ed
React i on
Name
A default name is provided which may be changed. The
previous view shows t he name as Rxn- 1.
Component s The component s t o be react ed. A minimum of t wo
component s are required. You must specify a minimum of
one react ant and one product for each react ion you include.
Use t he drop- down list t o access t he available component s.
The Molecular Weight of each component is aut omat ically
displayed.
St oi chi omet r
i c Coef f i ci ent
Necessary for every component in t he react ion. The
St oichiomet ric Coefficient is negat ive for a react ant and
posit ive for a product . You may specify t he coefficient for an
inert component as 0, which, for t he Conversion react ion, is
t he same as not including t he component in t he t able. The
St oichiomet ric Coefficient does not have t o be an int eger;
fract ional coefficient s are accept able.
When you have supplied
all of t he required
informat ion for t he
Conversion React ion, t he
st at us bar ( at t he bot t om
right corner) will change
from Not Ready t o Ready.
The React ion Heat value is
calculat ed and displayed
below t he Balance Error. A
posit ive value indicat es
t hat t he react ion is
endot hermic.
React i ons 5- 9
5- 9
Basis Tab
The Basis t ab of a conversion react ion is shown in t he figure below:
On t he Basis t ab, you must supply t he following informat ion:
Fi gur e 5. 4
Requi r ed I nput Descr i pt i on
Base Component Only a component t hat is consumed in t he react ion ( a
react ant ) may be specified as t he Base Component
( i. e., a react ion product or an inert component is not a
valid choice) . You can use t he same component as t he
Base Component for a number of react ions, and it is
quit e accept able for t he Base Component of one
react ion t o be a product of anot her react ion.
You have t o add t he
component s t o t he
react ion before t he Base
Component can be
specified.
5- 10 React i ons
5- 10
5. 3. 3 Equilibrium React ion
The Equilibrium React ion comput es t he conversion wit h t he r eact ion
equilibrium paramet ers and st oichiomet ric const ant s you provide.
The Equilibrium const ant can be expressed as follows:
Rx n Phase The phase for which t he specified conversions apply.
Different kinet ics for different phases can be modeled
in t he same react or. Possible choices for t he React ion
Phase are:
Ov er al l . React ion occurs in all Phases.
Vapour Phase. React ion occurs only in t he
Vapour Phase.
Li qui d Phase. React ion occurs only in t he Light
Liquid Phase.
Aqueous Phase. React ion occurs only in t he
Heavy Liquid Phase.
Combi ned Li qui d. React ion occurs in all Liquid
Phases.
Ov er al l Combi ned. uses t he mixt ure composit ion
of t he Basis and allows solid component s t o be
react ant s.
Conver si on
Funct i on
Par amet er s
Conversion percent age can be defined as a funct ion of
react ion t emperat ure according t o t he following
equat ion:
This is t he percent age of t he Base Component
consumed in t his react ion. The value of Conv. ( %)
calculat ed from t he equat ion is always limit ed wit hin
t he range of 0.0 and 100%.
The act ual conversion of any react ion is limit ed t o t he
lesser of t he specified conversion of t he base
component or complet e consumpt ion of a limit ing
react ant .
React ions of equal ranking cannot exceed an overall
conversion of 100%.
To def i ne a const ant val ue f or conv er si on per cent age, ent er
a conver si on ( % ) val ue f or Co onl y . Negat i v e v al ues f or C1
and C2 means t hat t he conver si on dr ops w i t h i ncr eased
t emper at ur e and vi ce ver sa.
( 5. 3)
Requi r ed I nput Descr i pt i on
Sequent ial React ions may
be modelled in one
react or by specifying t he
sequent ial order of
solut ion. See React ion
Rank, in Sect i on 5. 4 -
React i on Set s.
Conv Co C1 T C2 T
2
+ + =
K BASE | |
e
j
( )
v
j
j 1 =
N
c
[
=
React i ons 5- 11
5- 11
where:
K = Equilibrium const ant
[ BASE] e
j
= Basis ( i. e. concent rat ion) for component j at equilibrium
v
j
= St oichiomet ric coefficient for t he j
t h
component
N
c
= Number of component s ( solid component s are skipped unless
Phase= OverallCombined)
Solid component s can part icipat e in an equilibrium react ion but t hey do
not ent er int o t he definit ion of t he equilibrium K const ant above, unless
Phase of OverallCombined has been select ed.
When Phase is select ed as OverallCombined, t he mole or mass fract ion/
concent rat ion of t he component in t he overall mixt ur e ( not specific
phases) is used. While t his is a deviat ion from most research, it does
provide a simpler approach t o modelling react ions. This approach is
necessary for equilibrium react ions involving solids, which could never
be in t he liquid or vapour phase, if a solid component may be a limit ing
react ant . The limit ing solid react ant nat urally diminishes t he react ion
ext ent because it has an effect on t he equilibrium.
The equilibrium const ant ln( K) may be considered fixed, or calculat ed
as a funct ion of t emperat ure:
where:
Alt ernat ively, you may supply t abular dat a ( equilibrium const ant versus
t emperat ure) , and UniSim Design aut omat ically calculat es t he
equilibrium paramet ers for you. Ln( K) may also be det ermined from t he
Gibbs Fr ee Energy.
St oichiomet ry Tab
The St oichiomet ry t ab for a equilibrium react ion is shown in t he figure
( 5. 4)
When you hav e suppl i ed al l of t he r equi r ed i nf or mat i on f or
t he Equi l i br i um React i on, t he st at us bar ( at t he bot t om r i ght
cor ner ) changes f r om Not Ready t o Ready .
This equat ion is only valid
when BASE ( i. e.,
concent rat ion) is at
equilibrium composit ion.
Ln Keq ( ) a b + =
a A
B
T
-- C T ( ) ln D T + + + =
b E T
2
F T
3
G T
4
H T
5
+ + + =
5- 12 React i ons
5- 12
below:
For each react ion, you must supply t he following informat ion:
Basis Tab
The Basis t ab for an equilibrium react ion cont ains t wo groups, t he Basis
and t he Keq Source, which are shown in t he figure below
Fi gur e 5. 5
I nput Requi r ed Descr i pt i on
React i on Name A default name is provided, which may be changed by
simply select ing t he field and ent ering a new name.
Component s A minimum of t wo component s is necessary. You must
specify a minimum of one react ant and one product for
each react ion you include. The Molecular Weight of
each component is aut omat ically displayed.
St oi chi omet r i c
Coef f i ci ent
For every component in t his react ion. The
St oichiomet ric Coefficient is negat ive for a react ant
and posit ive for a product . You may specify t he
coefficient for an inert component as 0. The
St oichiomet ric Coefficient need not be an int eger;
fract ional coefficient s are accept able.
Fi gur e 5. 6
React i ons 5- 13
5- 13
The Basis group requires t he following informat ion:
The Keq Source gr oup cont ains four radio but t ons and a checkbox.
By select ing t he appropriat e radio but t on, you can select one of
four opt ions as t he Keq Source for t he equilibrium react ion.
I f t he Aut o Det ect checkbox is checked, UniSim Design
aut omat ically changes t he Keq Source, depending on t he Keq
informat ion you provide. For example, if you ent er a fixed
equilibrium const ant , t he Fixed Keq radio but t on is aut omat ically
select ed. I f you lat er add dat a t o t he Table t ab, t he Keq vs. T
Table radio but t on is aut omat ically select ed.
Keq Tab
Depending on which opt ion was select ed in t he Keq Source group ( from
t he Basis t ab) , t he Keq t ab will display t he appr opriat e informat ion.
The following t able out lines each of t he Keq source opt ions and t he
Basi s From t he drop- down list in t he cell, select t he Basis for
t he react ion. For example, select Part ial Pressure or
Act ivit y as t he basis.
React i on Phase The possible choices for t he React ion Phase, accessed
from t he drop- down list , are t he VapourPhase and
LiquidPhase or OverallCombined.
Mi ni mum
Temper at ur e and
Max i mum
Temper at ur e
Ent er t he minimum and maximum t emperat ures for
which t he react ion expressions are valid. I f t he
t emperat ure does not st ay wit hin t he specified bounds,
a warning message alert s you.
Basi s Uni t s Select t he appropriat e unit s for t he Basis from t he
drop- down list .
5- 14 React i ons
5- 14
respect ive view on t he Keq t ab.
Approach Tab
Under cert ain process condit ions, an equilibrium react ion may not ,
Opt i on Descr i pt i on Vi ew on Keq Tab
Ln( Keq)
equat i on
Ln( Keq) , assumed t o be a funct ion of t emperat ure
only, is det ermined from t he following equat ion:
where:
A, B, C, D, E, F, G, H = t he const ant s of t he
correlat ion.
Gi bbs
Fr ee
Ener gy
The equilibrium const ant is det ermined from t he
default UniSim Design pure component Gibbs Free
Energy ( G) dat abase and correlat ion.
The correlat ion and dat abase values are valid/ accurat e
for a t emperat ure ( T) range of 25C t o 426. 85C.
I f a wider range of G-T correlat ion is required, t he user
can clone t he library component and input t he
component s Gibbs Free Energy correlat ion t o
t emperat ures beyond t he default t emperat ure limit .
Fi x ed K I n t his case, t he equilibrium const ant Keq is considered
t o be fixed, and is t hus independent of t emperat ure.
You may specify eit her Keq or Ln( Keq) on t he Keq t ab.
Check t he Log Basis box t o specify t he equilibrium
const ant in t he form Ln( Keq) .
K v s. T
Tabl e
On t he Keq t ab, you can provide t emperat ure and
equilibrium const ant dat a. UniSim Design est imat es
t he equilibrium const ant from t he pairs of dat a which
you provide and int erpolat es when necessary. For each
pair of dat a t hat you provide UniSim Design calculat es
a const ant in t he Ln( K) equat ion. I f you provide at
least 4 pairs of dat a, all four const ant s A, B, C and D
are est imat ed.
The const ant s may be changed even aft er t hey are
est imat ed from t he pairs of dat a you provide, simply
by ent ering a new value in t he appropriat e cell. I f you
lat er want t o revert t o t he est imat ed value, simply
delet e t he number in t he appropriat e cell, and it is
recalculat ed.
The t erm R2 gives an indicat ion of t he error or
accuracy of t he Ln( K) equat ion. I t is equal t o t he
regression sum of squares divided by t he t ot al sum of
squares, and is equal t o one when t he equat ion fit s t he
dat a perfect ly.
You can also provide t he maximum ( T Hi) and
minimum ( T Lo) t emperat ures applicable t o t he Ln( K)
relat ion. The const ant s are always calculat ed based on
t he t emperat ure range you provide. I f you provide
values in t he K Table which are out side t he
t emperat ure range, t he calculat ion of t he const ant s is
not affect ed.
Ln Keq ( ) a b + =
a A
B
T
-- C T ( ) ln D T + + + =
b E T
2
F T
3
G T
4
H T
5
+ + + =
React i ons 5- 15
5- 15
act ually reach equilibrium. The Equilibrium react ion set uses t wo t ypes
of approach, Fract ional and Temperat ure, t o simulat e t his t ype of
sit uat ion. You may select eit her one or bot h t ypes of approaches for use
in t he simulat ion.
The Approach t ab cont ains t wo groups, t he Fract ional Approach and
Temperat ur e Approach.
Bot h t he Fract ional Approach and Temperat ure Approach met hods can
be used t o simulat e an Equilibrium react ion t hat is a depart ure fr om
equilibrium.
For t he Temperat ure Approach met hod, t he UniSim Design react ion
solver will t ake int o account t he heat of react ion according t o t he
equat ions list ed. The dir ect ion of nonequilibrium depart ure depends on
whet her t he react ion is endot hermic or exot her mic.
The Fract ional Appr oach met hod is an alt ernat ive t o t he Temperat ure
Appr oach met hod and is defined according t o t he following equat ion:
Equat i on ( 5. 5) indicat es t hat Kconst is act ually used in t he equilibrium
react ion calculat ion. Therefore, t he act ual react ion ext ent is only a
percent age of t he equilibrium react ion ext ent of t he react ion. I n t he
solver, t he value of Approach% is limit ed bet ween 0 and 100%.
Fi gur e 5. 7
Temper at ur e Appr oach i s not r el evant f or a f i x ed Keq sour ce
and t hus t he gr oup does not appear w hen Fi x ed Keq i s
sel ect ed f r om t he Basi s t ab.
( 5. 5) Kconst Keq A pproach% =
5- 16 React i ons
5- 16
Library Tab
The Library t ab allows you t o add a pre- defined react ion from t he
UniSim Design Library. The component s for t he select ed Librar y
react ion are aut omat ically t ransferred t o t he Rxn Component s group of
t he React ion Manager.
When you select a react ion, all dat a for t he react ion, including t he
st oichiomet ry, basis, and Ln( K) paramet ers, are t ransferred int o t he
appropriat e locat ion on t he Equilibrium React ion propert y view. To
access a library react ion, highlight it from t he Library Equilibrium Rxns
group and click t he Add Library Rxn but t on.
5. 3. 4 Kinet ic React ion
To define a Kinet ic React ion, it is necessary t o specify t he forward
Arrhenius Paramet ers ( t he reverse is opt ional) , t he st oichiomet ric
coefficient s for each component , and t he for ward ( and reverse) react ion
orders. An it erat ive calculat ion occurs, t hat requires t he Solver t o make
init ial est imat es of t he out let composit ions. Wit h t hese est imat es, t he
rat e of react ion is det ermined. A mole balance is t hen performed as a
check on t he rat e of react ion. I f convergence is not at t ained, new
est imat es are made and t he next it erat ion is execut ed.
Fi gur e 5. 8
When K Tabl e cont ai ns dat a i nput , t he l i br ar y r eact i on
sel ect i on w i l l be bl ock ed. You must cl i ck t he Er ase Tabl e
but t on on t he Keq t ab and bef or e y ou can add a l i br ar y
r eact i on.
( 5. 6) r
A
k f BASIS ( ) k' f ' BASIS ( ) =
React i ons 5- 17
5- 17
Equat i on ( 5. 6) relat es t he rat e of react ion r
A
wit h t he r eact ion rat e
const ant s and t he basis ( e. g. - concent rat ion) . Equat i on ( 5. 7) is a
mole balance on t he unit operat ion; for st eady st at e solut ions, t he right
side is equal t o zero.
St oichiomet ry Tab
When t he Kinet ic React ion is select ed, t he following view is displayed:
For each react ion, you must supply t he following informat ion:
( 5. 7)
Fi gur e 5. 9
React i on Name A default name is provided, which may be changed at
any t ime.
Component s You must specify a minimum of one react ant and one
product for each react ion you include. Access t he
available component s using t he drop- down list . The
Molecular Weight of each Component is aut omat ically
displayed.
F
Ao
F
A
r
A
V d
V
}
+
dN
A
dt
------- =
informat ion for t he Kinet ic
React ion, t he st at us bar
( at t he bot t om right
corner) changes from Not
Ready t o Ready.
5- 18 React i ons
5- 18
Thermodynamic Consist ency
Crucial t o t he specificat ion of t he reverse react ion equat ion is
maint aining t hermodynamic consist ency so t hat t he equilibrium rat e
expression r et ains t he form of Equat i on ( 5. 3) . Failure t o do so may
produce erroneous result s from UniSim Design.
Consider t he previously ment ioned react ion:
wit h t he forward kinet ics following t he relat ionship:
Now suppose you want t o add t he reverse kinet ic react ion. Since t he
forwar d react ion is already known, t he or der of t he rever se react ion has
t o be derived in order t o maint ain t hermodynamic consist ency. Suppose
a generic kinet ic relat ionship is chosen:
Coef f i ci ent
Necessary for every component in t he react ion. The
and posit ive for a product . The St oichiomet ric
Coefficient need not be an int eger; fract ional
coefficient s are accept able. You may specify t he
coefficient for an inert component as 0, which in most
cases is t he same as not including t he component in
t he list . However, you may include component s t hat
have an overall st oichiomet ric coefficient of zero and a
non-zero order of react ion ( i.e., a component t hat
might play t he role of a cat alyst ) .
For w ar d and
Rever se Or der s
These are react ion orders. UniSim Design init ially fixes
t he orders of react ion according t o t he corresponding
st oichiomet ric coefficient . These may be modified by
direct ly ent ering t he new value int o t he appropriat e
cell. For inst ance, in t he following react ion:
t he kinet ic rat e law is
When t he st oichiomet ric coefficient s are ent ered for
t he react ion, UniSim Design set s t he forward orders of
react ion for CO and Cl
2
at 1. Simply ent er 1. 5 int o t he
Forward Order cell for Cl
2
t o correct ly model t he
react ion order.
( 5. 8)
( 5. 9)
CO Cl
2
+ COCl
2
r
CO
k CO | | Cl
2
| |
3 2
=
CO Cl
2
COCl
2
+
rate
forward
k
f
CO | | Cl
2
| |
3 2
=
rate
backward
k
r
CO | |
o
Cl
2
| |
|
COCl
2
| |
=
React i ons 5- 19
5- 19
where:
= t he unknown values of t he order of t he t hree component s
Equilibrium is defined as t he moment when:
The equilibrium const ant K is t hen equal t o:
To maint ain t he form of t he equilibrium equat ion seen in Equat i on
( 5.3) , K is also equal t o:
Now combining t he t wo relat ionships for K found in Equat i on ( 5. 10)
and Equat i on ( 5. 11) :
To maint ain t hermodynamic consist ency: must be 0, must be 0. 5
and must be equal t o 1.
Basis Tab
The Basis t ab for a kinet ic react ion is shown below:
(5.10)
(5.11)
(5.12)
Fi gur e 5. 10
o | , ,
rate
forward
rate
backward
0 =
K
k
f
k
r
---
CO | |
o
Cl
2
| |
|
COCl
2
| |
CO | | Cl
2
| |
3 2
------------------------------------------ = =
K
COCl
2
| |
CO | | Cl
2
| |
-------------------- =
CO | |
o
Cl
2
| |
|
COCl
2
| |
CO | | Cl
2
| |
3 2
------------------------------------------
COCl
2
| |
CO | | Cl
2
| |
-------------------- =
o |
5- 20 React i ons
5- 20
On t he Basis t ab, t he following paramet ers may be specified:
Paramet ers Tab
On t he Paramet ers t ab, you may specify t he forwar d and reverse
paramet ers for t he Arrhenius equat ions. These paramet ers are used in
t he calculat ion of t he forward and reverse react ion const ant s.
The react ion rat e const ant s are a funct ion of t emperat ure according t o
Basi s View t he drop- down list in t he cell t o select t he Basis
for t he react ion. I f, for inst ance, t he rat e equat ion is a
funct ion of t he part ial pressures, select Part ial Pressure
as t he Basis.
quit e accept able for t he Base Component of one
react ion t o be a product of anot her react ion.
React i on Phase The phase for which t he kinet ic rat e equat ions apply.
Different kinet ic rat e equat ions for different phases can
be modeled in t he same react or. Possible choices for
t he React ion Phase, available in t he drop- down list ,
are: Overall, VapourPhase, LiquidPhase,
AqueousPhase, CombinedLiquid and OverallCombined.
OverallCombined uses t he mixt ure composit ion of t he
Basis and allows solid component s t o be react ant s.
Mi ni mum
Temper at ur e and
Max i mum
Temper at ur e
which t he forward and reverse react ion Arrhenius
equat ions are valid. I f t he t emperat ure does not
remain wit hin t hese bounds, a warning message alert s
you during t he simulat ion.
drop- down list .
Rat e Uni t s Select t he appropriat e unit s for t he rat e of react ion
from t he drop- down list .
Fi gur e 5. 11
React i ons 5- 21
5- 21
t he following ext ended form of t he Ar rhenius equat ion:
where:
k = forward react ion rat e const ant
k' = reverse react ion rat e const ant
A = forward react ion Frequency Fact or
A' = reverse react ion Frequency Fact or
E = forward react ion Act ivat ion Energy
E' = reverse react ion Act ivat ion Energy
= forward ext ended react ion rat e const ant
= reverse ext ended react ion rat e const ant
R = I deal Gas Const ant ( value and unit s dependent on t he unit s
chosen for Molar Ent halpy and Temperat ure)
T = Absolut e Temperat ure
5. 3. 5 Het erogeneous Cat alyt ic
React ion
UniSim Design provides a het erogeneous cat alyt ic react ion kinet ics
model t o describe t he rat e of cat alyt ic react ions involving solid cat alyst .
The rat e equat ion is expressed in t he general form according t o Yang
and Hougen ( 1950) :
Since t hese t ypes of react ions involve surface react ion t oget her wit h
(5.13)
(5.14)
I f t he Ar r heni us coef f i ci ent , A i s equal t o zer o, t her e i s no
r eact i on. I f Ar r heni us coef f i ci ent s E and ar e zer o, t he r at e
const ant i s consi der ed t o be f i x ed at a val ue of A f or al l
t emper at ur es.
(5.15)
k A
E
RT ( )
--------
)
`

T
|
exp =
k' A'
E'
RT
-----
)
`

T
|'
exp =
A, E, , are t he
Arrhenius Paramet ers for
t he forward react ion. A' ,
E' , and are t he
Arrhenius Paramet ers for
t he reverse react ion.
I nformat ion for t he
reverse react ion is not
required.
|
|'
|
|'
|
r
kinetic term ( ) potential term ( )
adsorption term ( )
----------------------------------------------------- =
5- 22 React i ons
5- 22
adsorpt ion ( and desorpt ion) of react ant s and pr oduct s, t he result ing
rat e expression will be st rongly mechanism dependent .
Consider t he following simple react ion:
Depending on t he react ion mechanism, it s react ion rat e expression
( ignoring reverse rat e of react ion) could be:
where:
K
*
= t he adsorpt ion rat e const ant for component *
k
+
= t he forward react ion rat e const ant
k = react ion rat e const ant for oxidat ion of hydrocarbon
k* = react ion rat e const ant for surface re- oxidat ion
UniSim Design has provided a general form, as follows, t o allow user t o
build in t he form of rat e expression t hey want t o use.
where:
k
f
and k
r
= t he Rat e Const ant s of t he forward and reverse kinet ic rat e
expressions
K

= t he absorpt ion rat e const ant
M = number of absorbed react ant s and product s plus absorbed inert
species
Langmui r -
Hi nshel w ood Model
(5.16)
El ey - Ri deal Model (5.17)
Mar s- v an Kr ev el en
Model
(5.18)
(5.19)
aA bB cP +
r
k
+
K
A
K
B
C
A
C
B
1 K
A
C
A
K
B
C
B
K
P
C
P
+ + + ( )
2
----------------------------------------------------- =
r
k
+
K
B
C
A
C
B
1 K
B
C
B
K
P
C
P
+ + ( )
------------------------------------ =
r
kC
A
1 a b ( ) k k
-
( )C
A
C
B
n
+
------------------------------------------- =
r
k
f
C
i
o
i
i 1 =
Reactants
[
k
r
C
j
|
j
j 1 =
Products
[
1 K
k
C
g
kg
g 1 =
M
[
)

`

k 1 =
M
+
\ .
|
|
|
| |
n
-------------------------------------------------- =
React i ons 5- 23
5- 23
The rat e const ant s k
f
, k
r
and K
k
are all in Ar rhenius form. You are
required t o provide t he Ar rhenius paramet er s ( pre- exponent ial fact or A
and act ivat ion energy E) for each of t hese const ant s.
You may have t o group const ant s, for example in Equat i on ( 5. 16) , k
f
= k
+
K
A
K
B
. You must t ake care in input t ing t he correct values of t he
Arrhenius equat ion. Also not e t hat no default values are given for t hese
const ant s.
The Het erogeneous Cat alyt ic React ion opt ion can be used in bot h CSTR
and PFR react or unit operat ions. A t ypical React ion Set may include
mult iple inst ances of t he Het erogeneous Cat alyt ic React ion.
St oichiomet ry Tab
When t he Het erogeneous Cat alyt ic React ion is select ed, t he following
view is displayed:
For each cat alyt ic react ion, you must supply t he following informat ion:
Fi gur e 5. 12
React i on Name A default name is provided, which may be changed.
product for each react ion you include. Open t he drop-
down list in t he cell t o access all of t he available
component s. The Molecular Weight of each component
is aut omat ically displayed.
Coef f i ci ent
Necessary for every component in t his react ion. The
coefficient for an inert component as 0, which in t his
case is t he same as not including t he component in t he
list .
5- 24 React i ons
5- 24
Basis Tab
The Basis t ab for a cat alyt ic react ion is shown below:
Numerat or Tab
The Numerat or t ab is specified in much t he same way as you would
specify a t ypical UniSim Design Kinet ic React ion. The Numerat or t ab is
Fi gur e 5. 13
Basi s Open t he drop- down list in t he cell t o select t he Basis
for t he react ion. For example, select Part ial Pressure or
Molar Concent rat ion as t he basis.
accept able for t he Base Component of one react ion t o
be a product of anot her react ion.
React i on Phase The phase for which t he kinet ics apply. Different
kinet ics for different phases can be modeled in t he
same react or. Possible choices for t he React ion Phase
( available in t he drop- down list ) are Overall,
VapourPhase, LiquidPhase, AqueousPhase,
CombinedLiquid and OverallCombined.
Mi ni mum
Temper at ur e and
Max i mum
Temper at ur e
remain in t hese bounds, a warning message alert s you
during t he calculat ion.
drop- down list .
Kinet ic react ion
specificat ions see Sect i on
5. 3. 4 - Ki net i c
React i on.
React i ons 5- 25
5- 25
shown below:
You must supply t he forward and reverse ( opt ional) paramet ers of t he
ext ended Arrhenius equat ion. The forward and reverse react ion rat e
const ant s are calculat ed from t hese values. I n addit ion t o t he rat e
const ant s, you may also specify t he react ion order of t he various
component s for bot h t he forward and reverse react ions. This is done by
select ing t he Component s field of t he React ion Order cell mat rix, and
select ing t he appr opriat e component from t he drop- down list and
ent ering values for t he Forward and/ or Rever se or ders.
When specifying Forward and Reverse orders it is import ant t o maint ain
t hermodynamic consist ency. For more informat ion on t hermodynamic
consist ency see Sect i on 5. 3.4 - Ki net i c React i on, Thermodynamic
Consist ency.
Denominat or Tab
The Denominat or t ab for a cat alyt ic react ion is shown in t he following
figure:
Fi gur e 5. 14
Fi gur e 5. 15
5- 26 React i ons
5- 26
The Denominat or t ab cont ains t he Component Exponent s mat r ix in
which each row represent s a denominat or t erm. The A and E columns
are for t he pre- exponent ial fact or and t he act ivat ion energy,
respect ively for t he adsorpt ion t erm ( K) .
The remaining columns are used t o specify t he exponent s ( ) of t he
absorbed component s ( C
g
) . I n order t o add a t erm t o t he denominat or
of t he kinet ic expression, you must act ivat e t he row of t he mat rix
cont aining t he < empt y> message and add t he relevant equat ion
paramet er values. The Delet e Term but t on is provided t o delet e t he
select ed row ( or corresponding t erm) in t he mat r ix. The overall
exponent t erm n is specified in t he Denominat or Exponent field.
5. 3. 6 Simple Rat e React ion
The Simple Rat e React ion is also similar t o t he Kinet ic React ion, except
t hat t he reverse react ion rat e expression is derived fr om equilibrium
const ant expression.
St oichiomet ry Tab
When t he Simple Rat e React ion is select ed t he following view is
displayed.
(5.20)
Fi gur e 5. 16
1 K
k
C
g
kg
g 1 =
M
[
)

`

k 1 =
M
+
\ .
|
|
|
| |
n
kg
informat ion for t he
Simple Rat e React ion, t he
st at us bar ( at t he bot t om
right corner) will change
from Not Ready t o Ready.
React i ons 5- 27
5- 27
For each react ion, supply t he following informat ion:
Basis Tab
The Basis t ab for t he simple rat e react ion is shown below:
Fi el d Descr i pt i on
React i on Name A default name is provided, which may be changed.
product for each react ion you include. Open t he drop-
down list in t he cell t o access all of t he available
component s. The Molecular Weight of each component
is aut omat ically displayed.
Coef f i ci ent
Necessary for every component in t his react ion. The
coefficient for an inert component as 0, which in t his
case is t he same as not including t he component in t he
list .
Fi gur e 5. 17
Basi s Open t he drop- down list in t he cell t o select t he Basis
for t he react ion. For example, select Part ial Pressure or
Molar Concent rat ion as t he basis.
accept able for t he Base Component of one react ion t o
be a product of anot her react ion.
5- 28 React i ons
5- 28
Paramet ers Tab
The Paramet ers t ab for t he simple rat e react ion is shown below:
The forward react ion rat e const ant s are a funct ion of t emperat ure
according t o t he following ext ended form of t he Arrhenius equat ion:
where:
k = forward react ion rat e const ant
A = forward react ion Frequency Fact or
E = forward react ion Act ivat ion Energy
= forward ext ended react ion rat e const ant
React i on Phase The phase for which t he kinet ics apply. Different
kinet ics for different phases can be modeled in t he
same react or. Possible choices for t he React ion Phase,
available in t he drop- down list , are Overall,
VapourPhase, LiquidPhase, AqueousPhase,
CombinedLiquid and OverallCombined.
Mi ni mum
Temper at ur e and
Max i mum
Temper at ur e
remain in t hese bounds, a warning message alert s you
during t he simulat ion.
drop- down list .
Fi gur e 5. 18
(5.21)
k A
E
RT
----- T
|
exp =
|
React i ons 5- 29
5- 29
R = I deal Gas Const ant
T = Absolut e Temperat ure
The reverse equilibrium const ant K' is considered t o be a funct ion of
t emperat ure only:
where:
A' , B' , C' , D' = t he reverse equilibrium const ant s
You must supply at least one of t he four reverse equilibrium const ant s.
5. 4 React ion Set s
All React ion Set s cr eat ed wit hin t he React ion Manager become available
for at t achment t o your react or operat ions in t he flowsheet . React ion
Set s may cont ain more t han one react ion. There is limit ed flexibilit y for
t he mixing of react ion t ypes wit hin a React ion Set . You can have
Equilibrium and Kinet ic react ions wit hin a single React ion Set , but you
must have a dist inct React ion Set for conversion react ions.
UniSim Design provides t he Global Rxn Set , which cont ains all
compat ible react ions t hat you have defined in t he case. I f you only add
Kinet ic and Equilibrium react ions, or exclusively Conversion react ions t o
t he case, all react ions are act ive wit hin t he Global Rxn Set . However, if
you add an incompat ible mix of react ions ( i. e., Conversion and Kinet ic) ,
only t he t ype of react ions t hat are compat ible wit h t he first inst alled
react ion are act ive in t he Global Rxn Set .
The same react ion can be act ive in mult iple react ion set s. A new set
can be added from t he React ion Manager by select ing t he Add Set
but t on.
I f Ar r heni us coef f i ci ent A i s equal t o zer o, t her e i s no
r eact i on. I f Ar r heni us coef f i ci ent s E and ar e equal t o zer o,
t he r at e const ant i s consi der ed t o be f i x ed at a val ue of A f or
al l t emper at ur es.
(5.22)
|
K' ln A'
B'
T
---- C' T ( ) ln D'T + + + =
I f only one t ype of
react ion is used, all
react ions are act ive in t he
Global Rxn Set , t hereby
eliminat ing t he need t o
explicit ly define a new
React ion Set .
5- 30 React i on Set s
5- 30
5. 4. 1 Manipulat ing React ion Set s
All React ion Set manipulat ions are conduct ed in t he React ion Set s
group of t he React ions t ab of t he Basis Manager. The following but t ons
are available in t he React ion Set s group t o manipulat e react ion set s:
5. 4. 2 React ion Set View
When you add a new set , or view an exist ing one, t he React ion Set view
appears as shown below.
Vi ew Set Displays t he propert y view for t he highlight ed react ion set .
Add Set Adds a react ion set t o t he list of react ion set s and opens it s
propert y view.
Del et e Set Removes t he highlight ed react ion set ( s) from t he React ion
Manager. You must confirm your act ion t o delet e a react ion
set .
Copy Set Duplicat es t he highlight ed react ion set ( s) .
I mpor t Set Opens a react ion set from disk int o t he current case.
Ex por t Set Saves a react ion set t o disk for use in anot her case.
Add t o FP Accesses t he Add ' React ion Set Name' view, from which you
at t ach t he highlight ed react ion set ( s) t o a fluid package.
This but t on is available only when a React ion Set is
highlight ed in t he React ion Set s group.
Fi gur e 5. 19
When you right - click a
React ion Set in t he React ion
Set s group, you can select
View or Delet e from t he
Obj ect I nspect menu.
React i ons 5- 31
5- 31
The following t able describes t he feat ures cont ained wit hin t his view.
Feat ur e Descr i pt i on
Name A default React ion Set name is provided, which can be
changed.
Set Ty pe UniSim Design det ermines t he Set Type from t he react ion
t ypes in t he Act ive List . This field cannot be modified. The
React ion Set t ypes are Conversion, Kinet ic, Equilibrium,
and Mixed. A Mixed Set Type corresponds t o a React ion Set
cont aining bot h Kinet ic and Equilibrium react ions.
Sol ver
Met hod
The Solver met hod is available when dealing wit h Kinet ic
react ion set s. Several Solver Met hods are available from
t he drop- down list and explained below:
Def aul t . The React ion Solver at t empt s t o calculat e
t he solut ion using Newt on' s Met hod. I f t his is not
successful, it t hen uses t he Rat e I t erat ed and Rat e
I nt egrat ed Met hods. For most cases, it is best t o use
t he Default Solver Met hod.
New t on' s Met hod. This met hod usually converges
quickly by t aking t he derivat ive of t he funct ion using
t he current est imat es, and uses t hese result s t o obt ain
new est imat es.
Rat e I t er at ed. This met hod is a part ial Newt on' s
met hod, and assumes t hat t he off- diagonal element s
of t he Jacobian mat rix are equal t o zero. The Rat e
I t erat ed Met hod works well when t here is very lit t le
int eract ion bet ween react ions.
Rat e I nt egr at ed. This met hod int egrat es t he
react ion equat ions unt il all t ime derivat ives are zero.
The Rat e I nt egrat ed met hod is st able, but slow.
Aut o Sel ect ed. Same as Default .
Act i v e Li st React ions may be added t o t he Act ive List by posit ioning
t he cursor in t he Act ive List column and select ing an
exist ing React ion from t he drop- down list . You may also
t ype t he name of an exist ing react ion direct ly in t he cell
t hat shows < empt y> .
You can open t he propert y view for any react ion in t he
Act ive List by highlight ing it and clicking t he Vi ew Act i ve
but t on. Alt ernat ively, you may double- click on t he react ion
t o view it .
A react ion in t he Act ive List may be t ransferred t o t he
I nact ive List simply by select ing t he react ion and clicking
t he Mak e I nact i v e but t on.
5- 32
Advanced Feat ures
By clicking t he Advanced but t on, you can view t he Advanced react ion
I nact i v e Li st Exist ing react ions may be added t o t he I nact ive List by
posit ioning t he cursor in t he I nact ive List column and
select ing a React ion from t he drop- down list .
You can access t he propert y view for any react ion in t he
I nact ive List by highlight ing it and clicking t he Vi ew
I nact i v e but t on. You may also double- click on t he react ion
t o view it .
A react ion in t he I nact ive List may be t ransferred t o t he
Act ive List by select ing t he react ion and clicking t he Mak e
Act i v e but t on. I f t his react ion is not independent of ot her
react ions in t he Act ive List , an error message is displayed,
and t he react ion remains in t he I nact ive List .
Ex ampl e
Dependent [ react ions] means t hat t he t here are react ions
in t he React ionSet which are dependent each ot her. [ E. g.]
t he following t hree equilibrium react ions are dependent
each ot her: That is, React ion ( 3) is equivalent t o t he
result ant of React ion ( 1) plus react ion ( 2) .
2H2S + 3O2 = 2SO2 + 2H2O ( 1)
4H2S + 2SO2 = 4H2O + 3S2 ( 2)
2H2S + O2 = 2H2O + S2 ( 3)
Physically, t here is no meaning for equilibrium react ion ( 3)
in t he syst em t oget her wit h equilibrium react ion ( 1) and
( 2) . Mat hemat ically, it will creat e a singular mat rix t o t he
solver.
Oper at i ons
At t ached
All operat ions t o which t he React ion Set is at t ached are
list ed in t his column.
Feat ur e Descr i pt i on
You cannot have t wo
versions of t he same
react ion wit h different
rat e const ant s in t he
Act ive List .
React i ons 5- 33
5- 33
opt ions.
Wit hin t he Volume Cont inuat ion Paramet ers group, t he following
opt ions are available:
Fi gur e 5. 20
Vol ume
Cont i nuat i on
For most cases, it is not necessary t o select t his opt ion.
I n sit uat ions where convergence is not easily at t ained
( e. g., high react ion rat es) , check t he Volume
Cont inuat ion checkbox t o enable UniSim Design t o
more easily reach a solut ion. For Volume Cont inuat ion
calculat ions, UniSim Design ramps t he volume
st art ing from t he init ial volume fract ion t o t he final
volume fract ion in t he specified number of st eps. For
each successive st ep, t he previous solut ion is used as
t he init ial est imat e for t he next st ep.
I ni t i al Vol ume
Fr act i on
The default value is 1.0000e- 06. This is t he Volume
Fract ion at t he st art of t he calculat ions.
Number of St eps The default value is 10. I f t he solut ion does not
converge, increase t his value and re- run t he
simulat ion.
Cur r ent Par m
Val ue
This field displays t he current paramet er value.
Cur r ent St ep
Number
This field displays t he current st ep number.
Tr ace Level Provides a t race out put of t he calculat ions in t he Trace
Window. The t race level value corresponds t o t he level
of det ail t hat you see in t he Trace Window. You are
limit ed t o t he values 0, 1, 2, or 3.
5- 34
The paramet ers wit hin t he I nit ial Est imat e Generat ion Paramet er s
group are generally used wit h React ions t hat have a high degree of
int eract ion. You can also use t hese paramet ers t o give some assist ance
in obt aining t he final solut ion when t he react or operat ion fails t o
converge or when you have a large number of component s and
react ions. The paramet ers are described in t he following t able:
The React ion Solver Opt ion group allows you t o set t he number of
it erat ions and t he t olerance level. The opt ion depends on t he boundary
condit ion of t he react or operat ion which is used in t he react ion set . For
example, when a react or operat ion is used t o det ermine t he out let
t emperat ure, t he number of it erat ions and t olerance level are used in
t he react ion solver t o search for a solut ion.
Pr ev Sol ut i on as
Est i mat es
I t is necessary t o make an init ial est imat e of t he out let
composit ions t o obt ain t he proper solut ion. Check t his
checkbox if you want t o use t he previous solut ion as
t he init ial est imat e. This does not apply t o t he
conversion react ion, since t he specified conversion
det ermines t he out let composit ions.
Use I so and Adi a
Temp as Adi a Est
I f you calculat e a heat flow given a specific
t emperat ure, and t hen use t his heat flow as a spec
( delet ing t he t emperat ure specificat ion) , UniSim
Design uses t he previously calculat ed t emperat ure as
an est imat e for t he Adiabat ic calculat ion.
Dampi ng
Fact or
Default is 1.0, indicat ing t hat t here is no damping. You can
change t his value. Wit h a lower t he damping fact or, UniSim
Design uses smaller st eps ( slower and more st able) in
converging t owards t he solut ion.
Tol er ance This is t he t olerance set for t he Est imat e Generat ion. By
default , t his is set t o 0. 001. You are able t o change t his
value.
Max i mum
I t er at i ons
Maximum number of it erat ions t he int ial est imat ion rout ine
uses. There is no default value, and so you can set
what ever value is desired.
Max Numb of
I t er at i on
Cont rols t he maximum number of it erat ions specified
before t he react ion solver st ops searching for a solut ion. By
default , t he value is 200.
Tol er ance The specified t olerance level is t he relat ive error bet ween
t he energy balance equat ion and t he calculat ed value by
t he react ion solver in t he it erat ion. By default , t he value is
0.00001.
Accept best
Dy nami cs
Mode Sol ver
Resul t
The solver will search a result by reducing t he t olerance
when it erat ions reach t he maximum number of it erat ions
specified ( t his opt ion works only when t he case is in
dynamics mode) .
React i ons 5- 35
5- 35
React ion Rank
The Ranking but t on is visible only when t he React ion Set t ype is
Conversion. This opt ion aut omat ically handles most sit uat ions where
react ions are sequent ial:
allowing t he t hree react ions t o be modeled in a single react or.
However in sit uat ions wher e t here are compet ing react ions:
you can use t he Ranking fact or t o specify which conversion value
should be applied first . For example, if Rxn- 4 was ranked first , t he
specified conversion for Rxn- 5 would only be applied t o t he amount of
component B remaining aft er Rxn- 4 had run t o it s specified conversion.
To specify t he Ranking, you must do so from t he React ion Ranks view,
Uni Si m Desi gn assi gns def aul t r ank s t o mul t i pl e conver si on
r eact i ons by ex ami ni ng t he r eact ant s and pr oduct s. For
ex ampl e, y ou may have a r eact i on set cont ai ni ng t he
f ol l ow i ng:
1. CH
4
+ H
2
O CO+ 3H
2

2. CH
4
+ 2H
2
O CO
2
+ 4H
2
3. CH
4
+ 2O
2
CO
2
+ 2H
2
O
Uni Si m Desi gn not i ces t hat a pr oduct of React i on 3, H
2
O, i s
used as a r eact ant i n bot h React i ons 1 and 2. Si nce H
2
O may
not be avai l abl e unt i l React i on 3 has occur r ed, i t i s assi gned
a r ank of 0 and t he ot her r eact i ons ar e each gi ven t he def aul t
Rank of 1. The f eed composi t i on i s not t ak en i nt o account , as
React i on Rank s ar e assi gned pr i or t o ent er i ng t he Bui l d
Env i r onment .
Fi gur e 5. 21
I n t his case t he Rank
would be:
A B 1
B C 2
C D 3
A B
Rxn 1
B C
Rxn 2
C D
Rxn 3
A B + C
Rxn 4
B D + E
Rxn 5
5- 36
which cont ains t he following fields:
The but t ons along t he bot t om of t he React ion Ranks view have t he
following funct ions:
5. 4. 3 Export ing/ I mport ing a
React ion Set
Aft er a React ion Set is cust omized wit h react ions, it can be export ed t o
a file. The same React ion Set can t hen be used in anot her simulat ion
case by import ing t he file and at t aching it t o a fluid package. Highlight a
React ion Set in t he React ion Set s group of t he React ion Manager and
click t he Export Set but t on.
Select a file pat h ( t he default is usually sat isfact ory) and ent er a
filename wit h t he ext ension * .r st . Click t he Sav e but t on t o expor t t he
React i on This column shows all of t he react ions t o be ranked.
Rank Shows t he rank for each react ion, which is an int eger value.
The minimum value is 0 and t he maximum is equal t o t he
number of React ions ranked. Thus, when ranking t hree
sequent ial react ions, you may rank t hem 0- 1- 2 or 1- 2- 3;
bot h met hods give t he same result s. You may override t he
default values t hrough t he input of new values in t he
appropriat e cells.
User
Speci f i ed
I f you specify t he Rank of t he react ion, t his checkbox is
checked.
Cancel Closes t he view wit hout accept ing any changes t hat were
made.
Reset Reset s t he React ion Ranks t o t he int ernal default .
Accept Closes t he view, accept ing t he changes t hat were made.
Fi gur e 5. 22
You can set t wo or more
react ions t o have t he
same Rank; for inst ance,
t he ranks for Rxn- 1 and
Rxn- 2 may be 1, and t he
rank for Rxn- 3 may be 2.
React i ons 5- 37
5- 37
react ion set t o a file.
The I mport Set but t on allows you t o int r oduce an export ed React ion Set
int o a simulat ion case. Choose t he React ion Set file ( wit h t he ext ension
* .r st ) from t he list and select t he Open but t on. I f t he file is not list ed in
t he File Name field, an alt ernat e File Pat h may be needed.
5. 4. 4 Adding a React ion Set t o a
Fluid Package
To make a React ion Set available inside t he flowsheet , you must at t ach
it t o t he fluid package which is associat ed wit h t he flowsheet .
Highlight a react ion set in t he React ion Set s group of t he React ion
Manager and click t he Add t o FP but t on. The Add ' React ion Set Name'
view appears, where you can highlight a fluid package and click t he Add
Set t o Fluid Package but t on.
5. 4. 5 React ions in t he Build
Environment
When you are inside t he Main or Column Environment you can access
t he React ion Package view wit hout having t o ret urn t o t he Basis
Environment . Under Flowsheet in t he Main Menu, select React ion
Package.
When a React ion Set is at t ached t o a unit operat ion, you can access t he
React ion Set view or t he view( s) for t he associat ed React ion( s) direct ly
from t he propert y view of t he operat ion. Some of t he unit operat ions
t hat support react ions include t he React or operat ion ( conversion,
equilibrium, or kinet ic) , t he PFR, t he Separat or, and t he Column.
Fi gur e 5. 23
React i on Pack age of t he
Uni Si m Desi gn User
Gui de for more det ails.
Desi gn Oper at i on
Gui de for more
individual unit operat ions.
5- 38 Gener al i zed Pr ocedur e
5- 38
5. 5 Generalized Procedure
The following procedure out lines t he basic st eps for creat ing a react ion,
creat ing a react ion set , adding t he react ion t o t he react ion set and t hen
making t he set available t o t he flowsheet . Refer t o t he React ion
Package view, shown in Fi gur e 5. 1, as you follow t he pr ocedure:
1. Select React i on Pack age under Fl ow sheet in t he menu bar.
2. On t he React ion Package view, click t he Add Rx n but t on t o creat e a
new React ion.
3. A React ions view appears, from which you must select t he t ype of
react ion t o creat e. Select a react ion t ype and click t he Add
React i on but t on.
4. The propert y view for t he react ion t ype you select ed is displayed.
Complet e t he input for t he react ion unt il Ready appears as t he
st at us message. You can close t he React ion propert y view, if
desired.
5. On t he React ion Package view, click t he New Set but t on t o creat e a
React ion Set . The React ion Set view appears.
Fi gur e 5. 24
Fi gur e 5. 25
React i ons 5- 39
5- 39
6. I f desired, change t he Name of t he React ion Set t o bet t er ident ify it .
7. To at t ach t he newly cr eat ed react ion t o t he React ion Set , place t he
cursor in t he < empt y > cell of t he Act ive List column. Open t he
drop- down list in t he cell and select a r eact ion. The react ion
becomes at t ached t o t he React ion Set , as indicat ed by t he act ivat ed
checkbox in t he OK column.
8. Click t he Cl ose but t on on t he React ion Set view.
9. I n t he Av ai l abl e React i on Set s group of t he React ion Package
view, highlight t he name of t he newly creat ed React ion Set . Not ice
t hat t he at t ached react ion is list ed in t he Associ at ed React i ons
group.
10. Click t he Add Set but t on t o make t he React ion Set , and t hus t he
React ion, available t o unit operat ions in t he flowsheet . The new
React ion Set is displayed in t he Cur r ent React i on Set s group.
5. 6 React ions - Example
The following pr ocedure demonst rat es t he minimum st eps required for:
The addit ion of component s t o t he React ion Manager.
The creat ion of a react ion.
The addit ion of t he react ion t o a react ion set .
The at t achment of t he react ion set t o a fluid package.
5. 6. 1 Add Component s t o t he
React ion Manager
For t his example, it is assumed t hat a New Case is creat ed and a fluid
package is inst alled.
1. Wit hin t he fluid package, t he Peng Robinson propert y package is
select ed.
2. Wit hin t he component list , t he following set of component s are
select ed: H
2
O, CO, CO
2
, H
2
, O
2
, and CH
4
.
3. Go t o t he React i ons t ab of t he Simulat ion Basis Manager. The
select ed component s are present in t he Rxn Component s group.
5. 6. 2 Creat e a React ion
1. To inst all a react ion, click t he Add Rx n but t on.
2. From t he React ions view, highlight t he Conv er si on react ion t ype
and click t he Add React i on but t on. The Conversion React ion
propert y view appears.
Pack age Pr oper t y Vi ew
for det ails on inst alling a
fluid package.
React i ons for
informat ion concerning
react ion t ypes and t he
addit ion of react ions.
5- 40 React i ons - Ex ampl e
5- 40
3. On t he St oi chi omet r y t ab, select t he first row of t he Component
column in t he St oichiomet ry I nfo t able.
4. Select Met hane from t he drop- down list . The Mole Weight column
aut omat ically provides t he molar weight of met hane.
5. I n t he St oi ch Coef f field, ent er - 3 ( i. e., 3 moles of met hane is
consumed) .
6. Now define t he rest of t he St oichiomet ry t ab as shown in t he figure
below and click t he Bal ance but t on.
7. Go t o t he Basi s t ab and set Met hane as t he Base Component and
Conver sion t o 60% . The st at us bar at t he bot t om of t he propert y
view now shows a Ready st at us. Close t he pr opert y view.
5. 6. 3 Add t he React ion t o a
React ion Set
By default , t he Global Rxn Set is present wit hin t he React ion Set s gr oup
when you first display t he React ion Manager. However, for t his
procedure, a new React ion Set is creat ed:
1. Click t he Add Set but t on. UniSim Design provides t he name Set - 1
and opens t he React ion Set propert y view.
2. To at t ach t he newly cr eat ed React ion t o t he React ion Set , place t he
cursor in t he < empt y > cell under Act ive List .
3. Open t he drop- down list and select t he name of t he React ion ( Rxn-
1) . The Set Type corresponds t o t he t ype of React ion which you
have added t o t he React ion Set .
Fi gur e 5. 26
React i on Set s for det ails
concerning React ions
Set s.
React i ons 5- 41
5- 41
The st at us is now Ready.
4. Close t he view t o r et urn t o t he React ion Manager.
5. 6. 4 At t ach t he React ion Set t o a
Fluid Package
1. To at t ach t he react ion set t o t he fluid package, highlight Set - 1 in
t he React ion Set s group and click t he Add t o FP but t on.
2. The Add ' Set - 1' view appears, from which you highlight a fluid
package and click t he Add Set t o Fl ui d Pack age but t on.
3. Close t he view. Not ice t hat t he name of t he fluid package appears in
t he Assoc. Fluid Pkgs group when t he React i on Set is highlight ed
in t he React ion Set s group.
Fi gur e 5. 27
Fi gur e 5. 28
When a React ion Set is
at t ached t o a Fluid
Package, it becomes
available t o unit
operat ions wit hin t he
Flowsheet using t hat
part icular Fluid Package.
5- 42 React i ons - Ex ampl e
5- 42
Component Maps 6- 1
6- 1
6 Component Maps
6.1 I nt r oduct i on ............. ........................................................... .......... 2
6.2 Component Maps Tab ........................................................... .......... 2
6.2.1 Component Mapping Group .. .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 2
6.2.2 Collect ions Group . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 3
6.2.3 Maps for Collect ion Group . ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 3
6.3 Component Map Pr oper t y Vi ew ............................................ .......... 3
6- 2
On t he Component Maps t ab of t he Simulat ion Basis Manager, you can
map fluid component composit ion across fluid package boundaries.
Composit ion values for individual component s from one fluid package
can be mapped t o a different component in an alt ernat e fluid package.
This is usually done when dealing wit h hypot het ical oil component s.
Two previously defined fluid packages are required t o perform a
component mapping which is defined as a collect ion. One fluid package
becomes t he t arget component set and t he ot her becomes t he source
component set . Mapping is performed using a mat rix of source and
t arget component s. The t ransfer basis can be performed on a mole,
mass, or liquid volume basis.
6. 2 Component Maps Tab
The Component Maps t ab of t he Simulat ion Basis Manager is shown
below.
6. 2. 1 Component Mapping Group
The Component Mapping group defines t he source and t arget fluid
packages t o be mapped. Once t wo dist inct fluid packages are select ed,
t he Creat e Collect ion but t on creat es a collect ion in t he Collect ions
group.
Fi gur e 6. 1
Component Maps 6- 3
6- 3
6. 2. 2 Collect ions Group
The Collect ions group list s all t he component mapping collect ions
current ly available. You can change t he collect ion name by select ing t he
name you want t o edit and t yping in t he new name.
6. 2. 3 Maps for Collect ion Group
The Maps for Collect ion gr oup allows you t o manage your Component
Maps for each collect ion. The Collect ion drop- down list let s you select
t he collect ion maps t hat you want t o add, edit , or delet e. A default
collect ion map is added t o t his list and cannot be delet ed. To add a
Component Map based on t he current ly select ed collect ion, click t he
Add but t on. To view a Component Map, select it from t he list and click
t he View but t on. Bot h t he Add and View but t ons open t he Component
Map Propert y view. To delet e a Component Map, select t he map from
t he list and click t he Delet e but t on.
6. 3 Component Map Propert y
View
Each t ime a Component Map is creat ed or viewed via t he Component
Maps t ab of t he Simulat ion Basis Manager, t he Component Map
propert y view opens as shown below:
The Component Map pr opert y view allows you t o map t he source
Fi gur e 6. 2
6- 4 Component Map Pr oper t y Vi ew
6- 4
component s t o t he t arget component s in t he component mat r ix. Wit hin
t he mat rix, you can map all Specifiable ( in red) component mapping
values. The following t able describes all of t he opt ions found in t his
view.
Name Displays t he name of t he component map. The name
can be modified wit hin t he cell.
Vi ew Opt i ons The View Opt ions group provides you wit h t hree
opt ions in which t o view t he component mat rix.
Vi ew Al l . Displays all of t he source and t arget
component s in t he mat rix.
Vi ew Speci f i abl e. Displays only t he component s
t hat require values.
Tr anspose. Transposes t he component mat rix.
Component
Tr ansf er Opt i ons
The Component Transfer Opt ions group provides t wo
opt ions.
Unl ock al l Component s. Unlocks all of t he
component values, allowing you t o specify your
own values.
Tr ansf er Li k e Hy pot het i cal s. Aut omat ically
maps like hypot het icals.
Tr ansf er Hy pos by NBP. Aut omat ically maps
hypos by NBP. This opt ion is available when you
checked t he Transfer Like Hypot het icals checkbox.
Tr ansf er Basi s The Transfer Basis group provides t hree opt ions t hat
allow you t o define t he composit ion mapping basis:
Mole
Mass
Liq Volume
Mul t i pl e Speci f y Allows you t o specify a value t o one or more
component s at a t ime.
Cl one f r om
anot her Map
Allows you t o import values int o t he mapping mat rix
from anot her map.
Cl ear Al l Removes all of t he user defined informat ion from t he
mat rix.
Nor mal i ze Normalizes t he mapping mat rix.
User Pr oper t i es 7- 1
7- 1
7 User Propert ies
7.1 I nt r oduct i on ............. ........................................................... .......... 2
7.2 User Pr oper t y Tab ..... ........................................................... .......... 3
7.2.1 Adding a User Propert y ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 3
7.3 User Pr oper t y Vi ew ... ........................................................... .......... 4
7.3.1 Dat a Tab . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
7.3.2 Not es Tab .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
7- 2
On t he User Propert y t ab of t he Simulat ion Basis Manager, you can
creat e user proper t ies for use in t he Build Environment . A User Propert y
is any propert y t hat can be defined and subsequent ly calculat ed on t he
basis of composit ion.
When User propert ies are specified, t hey are used globally t hroughout
t he case. You can supply a User Propert y value for each component .
User pr opert ies can be modified for a specific component , fluid
package, or st ream using t he propert y edit or.
Specifying a User Propert y is similar t o supplying a value at t he
component level in t hat it is globally available t hroughout t he case,
unless it is specified ot herwise. I t is t he init ial user propert y value for
t he component in t he mast er component list . By select ing t he mixing
basis and mixing equat ion, t he t ot al User Propert y can be calculat ed.
Aft er a user propert y is defined, UniSim Design will t r eat it similarly as
any ot her int ernal propert y, such as molecular weight . To add it t o t he
Propert ies list on t he Worksheet t ab of a st ream propert y view, follow
t hese st eps:
1. Double click t he mat er ial st ream.
2. Click Propert ies page on t he Wooksheet t ab.
3. Click t he Append New Correlat ion icon in t he Propert y Correlat ion
Cont rols gr oup.
4. On t he Cor relat ion Picker view, click t he user propert y name under
t he Clone group.
5. Click t he Apply but t on.
I n addit ion, UniSim Design st ill support s t he old way of calculat ing user
propert ies t hrough user pr opert y ut ilit y, which can be accessed t hrough
Tools/ Ut ilit ies/ User Propert y/ Add Ut ilit y.
A word of caut ion on user propert y: Since t he user propert y value of a
st ream is based on t he individual user propert y values of it s
composit ion, UniSim Design may not be able t o calculat e t he user
propert y value of t he st ream if any of it s component s, especially t he
library component s, has undefined or empt y value for t he user
propert y. You may assign global user propert y values t o t he library
component s on t he user propert y definit ion view, or you may assign
different values for different fluid packages or st reams by launching t he
propert y edit or on t he fluid package or st ream composit ion view.
Refer t o Edi t Pr oper t i es
from Sect i on 1.2. 3 -
Mani pul at i ng t he
Sel ect ed Component s
Li st for more
propert y edit or.
7- 3
7. 2 User Propert y Tab
The User Propert y t ab of t he Simulat ion Basis Manager is shown below:
The available User Propert ies are list ed in t he User Propert ies gr oup.
The following User Propert y manipulat ion but t ons are available:
I n t he User Propert y Paramet ers group, all informat ion pert aining t o t he
highlight ed propert y in t he User Propert y group is displayed. You can
edit t he User Propert y paramet ers direct ly on t he Simulat ion Basis view
or click on t he View but t on for t he User Propert y view.
7. 2. 1 Adding a User Propert y
To add a user propert y, follow t he st eps below:
1. On t he User Propert y t ab of t he Simulat ion Basis Manager, click t he
Add but t on. The User Propert y view is displayed.
2. Provide a descript ive Name for t he user propert y on Simulat ion
Basis view.
Fi gur e 7. 1
Vi ew Edit t he current ly highlight ed User Propert y.
A User Propert y can also be added or viewed t hrough t he
Oi l Char act er i zat i on - User Pr oper t y t ab.
Add Creat e a new User Propert y.
Del et e Erase t he current ly highlight ed User Propert y. UniSim
Design will not prompt for confirmat ion when delet ing a
User Propert y, so be careful when you are using t his
command.
Refer t o Sect i on 7.3 -
User Pr oper t y Vi ew for
descript ions of t he User
Propert y Paramet ers.
7- 4 User Pr oper t y Vi ew
7- 4
3. I n t he User Propert y Paramet ers group, select a Mi x i ng Basi s using
t he drop- down list wit hin t he cell.
4. Select a Mi x i ng Rul e.
5. You can modify t he t wo Mixing Paramet ers ( F1 and F2) t o more
accurat ely reflect your propert y formula.
6. Select a Unit Type fr om t he filt ered drop- down list .
7. I nput init ial propert y values for each component .
7. 3 User Propert y View
Each t ime a User Propert y is creat ed t hrough t he User Propert y t ab of
t he Simulat ion Basis Manager, t he User Propert y view is displayed. The
User Proper t y view has t wo t abs, t he Dat a t ab and t he Not es t ab. All
informat ion regarding t he calculat ion of t he User Propert y is specified
on t he Dat a t ab.
7. 3. 1 Dat a Tab
On t he Dat a t ab, t he Basic user prop definit ion, and t he I nit ial user
propert y value groups are displayed.
Fi gur e 7. 2
7- 5
Basic User Propert y Definit ion Group
The following opt ions are available for Process t ype pr opert ies:
Mi x i ng Basi s You have t he following opt ions: Mole Fract ion, Mass
Fract ion, Liquid Volume Fract ion, Mole Flow, Mass Flow,
and Liquid Volume Flow.
All calculat ions are performed using composit ions in
UniSim Design int ernal unit s. I f you have specified a flow
basis ( molar, mass or liquid volume flow) , UniSim Design
uses t he composit ion as calculat ed in int ernal unit s for
t hat basis.
For example, a User Propert y wit h a Mixing Basis
specified as molar flow is always calculat ed using
composit ions in kg mole/ s, regardless of what t he current
default unit s are.
Mi x i ng Rul e Select from one of t hree mixing rules:
( 7. 1)
( 7. 2)
( 7. 3)
where:
P
mix
= t ot al user propert y value
P( i) = input propert y value for component
x( i) = component fract ion or flow, depending on
t he chosen Mixing Basis
I ndex = blended ( t ot al) index value
f1 and f2 are specified const ant s
Mi x i ng
Par amet er s
The mixing paramet ers f1 and f2 are 1. 00 by default . You
may supply any value for t hese paramet ers.
Uni t Ty pe This opt ion allows you t o select t he variable t ype for t he
user propert y.
For example, if you have a t emperat ure user propert y,
select t emperat ure in t he unit t ype using t he drop- down
list .
P
mix
( )
f 1
f 2 x i ( )P i ( )
f 1
( )
i 1 =
N
=
P
mix
( )
f 1
f 2 x i ( ) P i ( ) ( )
f 1
ln ( )
i 1 =
N
=
Index x i ( ) f 1 P i ( ) 10
f 2 P i ( )
+ ( )
i 1 =
N
=
7- 6
Mixing Rules
As list ed previously, t here ar e t hree mixing rules available when you ar e
defining a user propert y. Equat i on ( 7.1) and Equat i on ( 7. 2) are
relat ively st raight forward. The index mixing rule, Equat i on ( 7.3) , is
slight ly more complex.
Wit h t he index mixing rule, UniSim Design allows you t o combine
propert ies t hat are not inherent ly linear. A propert y is made linear
t hrough t he use of t he index equat ion.
Equat i on ( 7. 3) can be simplified int o t he following equat ions:
You supply t he individual component propert ies ( P
i
) and t he index
equat ion paramet ers ( i. e., f1 and f2) . Using Equat i on ( 7. 4) , UniSim
Design calculat es an individual index value for each supplied propert y
value. The sum of t he index values, which is t he blended index value, is
t hen calculat ed using t he Mixing Basis you have select ed ( Equat i on
( 7.5) ) .
The blended index value is used in an it erat ive calculat ion t o produce
t he blended propert y value ( P in Equat i on ( 7.6) ) . The blended
propert y value is t he value which will be displayed in t he user propert y
ut ilit y.
( 7. 4)
( 7. 5)
( 7. 6)
The form of your index
equat ion must resemble
t he UniSim Design index
equat ion such t hat you
can supply t he f1 and f2
paramet ers. Some
common propert ies which
can make use of t he I ndex
equat ion include R. O. N.,
Pour Point and Viscosit y.
Index
i
f 1 P i ( ) 10
f 2 P i ( )
+ =
Index x i ( ) Index
i
i 1 =
N
=
Index f1 P 10
f 2 P
+ =
7- 7
I nit ial User Propert y Values for All
Component s Group
The purpose of t his view is t o inst ruct UniSim Design how t he User
Propert y should be init ialized t hroughout t he case. Whenever t he value
of a User Propert y is request ed by t he User Propert y ut ilit y or by t he
column specificat ion, UniSim Design uses t he composit ion in t he
specified basis, and calculat e t he User Propert y value using your mixing
rule and paramet er s.
The values for pure component s are always used for t he propert y and
are not overwrit t en by t he synt hesis. The values for hypocomponent s
are only used if t he synt hesis of t he propert y can not be achieved. For
example, if t here are insufficient number of dat a point s. To specify a
Propert y Value, click on t he Edit component user propert y values
but t on.
Edit Component User Propert y Values
This view allows you t o edit init ial user pr opert y values for component s
in t he mast er component list .
Once propert y values are ent er ed or edit ed, click t he Submit but t on
which allows all values t o be modified at one t ime. The changes ar e
reflect ed on t he User Pr opert y view for each component .
Fi gur e 7. 3
User Propert y values can
be assigned t o
hypocomponent during
t he charact erizat ion of an
oil. Refer t o Sect i on
7. 2. 1 - Addi ng a User
Pr oper t y for more
informat ion.
Uni Si m Desi gn Ut i l i t i es
of t he Uni Si m Desi gn
more informat ion on t he
User Propert y ut ilit y.
Col umn of t he Uni Si m
Desi gn Oper at i ons
Gui de for informat ion on
t he User Propert y
specificat ion.
7- 8
7. 3. 2 Not es Tab
User Proper t ies for your own fut ure refer ence.
PVT Envi r onment 8- 1
8- 1
8 PVT Environment
8.1 I nt r oduct i on ............. ........................................................... .......... 2
8.2 PVT Envi r onment Manager ................................................... .......... 3
8.2.1 Engine Set up Tab . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
8.2.2 Reservoir Fluids Tab .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
8.3 Si mul at i on Basi s Manager .................................................... .......... 5
8.4 St r eam Pr oper t y Vi ew .......................................................... .......... 6
8- 2
The PVT Environment enables you t o use a t hird- part y PVT engine t o
creat e a t hermodynamic package which can be accessed seamlessly in
UniSim Design via UniSim Thermo.
There ar e t hree impor t ant t echnologies incorporat ed in t he process:
All informat ion associat ed wit h t hir d- part y PVT engines is
defined in a single locat ion, allowing for easy creat ion and
modificat ion of t he infor mat ion. The PVT Environment Manager
is accessible once you begin a new case in UniSim Design. The
PVT Environment Manager can be accessed from t he UniSim
Design Simulat ion Basis Manager and on t he t ool bar.
The UniSim Thermo PVT Harness is t he bridge linking t he UniSim
Design PVT Environment and t he t hird- part y PVT engine.
Each t hird- part y engine is capable of pr oviding UniSim Design
wit h at least one charact erized fluid per engine inst ance. I n
addit ion, each t hird part y engine will have a t uned propert y
package t hat t he user can use wit hin UniSim Design via UniSim
Thermo. However, t he propert y package opt ion is not available
for t he PVTSim dat abase link.
PVT Env i r onment 8- 3
8- 3
8. 2 PVT Environment
Manager
By clicking on t he Ent er PVT Env i r onment but t on from t he Simulat ion
Basis Manager, t he following propert y view appears:
There are t wo t abs in t he PVT Environment Manager:
Engine Set up
Reservoir Fluids
Fi gur e 8. 1
You can al so access t he PVT Envi r onment Manager by
cl i ck i ng on t he PVT Envi r onment i con on t he t ool bar .
PVT Environment icon
8- 4 PVT Env i r onment Manager
8- 4
8. 2. 1 Engine Set up Tab
The Engine Set up t ab allows you t o creat e or remove a PVT package.
When you click t he Add but t on from t he Engine Set up t ab, a new PVT
package is creat ed, and simult aneously t he Name field and Select ed
Engine list becomes act ive.
You can change t he name of t he PVT package by direct ly t yping in t he
Name field. You can specify an engine for t he package by select ing an
available t hird- part y engine from t he Select ed Engine list .
Current ly, I nfochem Mult iflash and Calsep PVTsim has been int egrat ed
int o UniSim Design as PVT engines. Short ly, DBR PVT Pro will be added
t o t he bundle.
You can configure t he propert y package for t he select ed PVT engine by
clicking t he Launch Engine but t on. Since t he PVT engines are t he links
t o t he t hird part y soft ware, please refer t o t he t hird part y soft ware
document at ion accordingly.
8. 2. 2 Reservoir Fluids Tab
The Reservoir Fluids t ab displays t he composit ion and propert y package
Fi gur e 8. 2
Current ly UniSim Design
support s PVTsi m version
16. 1 and above.
8- 5
for each reservoir fluid.
As you creat e a PVT package, a new reservoir fluid is added t o t he
Reservoir Fluid t ab. By default , each reservoir fluid is assigned t o t he
associat ed PVT engine as t he propert y package. You can re- assign a
UniSim Design propert y package t o t he reservoir fluid by unchecking
t he Use PVT Engine as Propert y Package checkbox in t he Associat ed
Basis group.
Click on t he Add New Basi s but t on t o open t he Fluid Package propert y
view, where you can select and define a desired UniSim Design
propert y package propert y for t he reservoir fluid. Click on t he Vi ew
Basi s but t on t o view t he specified PVT pr opert y package.
8. 3 Simulat ion Basis Manager
Once you have defined t he PVT propert y package, you can click on t he
Leav e Env i r onment but t on t o ret urn t o t he Simulat ion Basis Manager.
All component s, component list s, and fluid packages t hat are required
for t he PVT reservoir fluids are aut omat ically set up by t he PVT
Fi gur e 8. 3
Fi gur e 8. 4
Fl ui d Pack age for more
informat ion on defining a
UniSim Design propert y
package.
8- 6 St r eam Pr oper t y Vi ew
8- 6
Environment in t he Simulat ion Basis Manager.
You can ent er t he Simulat ion Environment t o st art modeling your case.
8. 4 St ream Propert y View
When a PVT propert y package is used, t he st ream propert y view has a
sub ply opt ion under Composit ion for t he reservoir fluids.
To apply a reservoir fluid t o a st ream, click on t he branch Pl us icon ,
and select Reservoir Fluid. A t able appears cont aining all t he reservoir
fluid specified in t he PVT Environment Manger.
Fi gur e 8. 5
Fi gur e 8. 6
8- 7
Select t he applicable reservoir fluid t hat is available in t he case, and
assign it t o t he st ream by clicking on t he Apply Reser voir Fluid t o
St r eam but t on. The st r eam will aut omat ically swit ch t o t he appropriat e
fluid package ( if necessary) and aut omat ically assign t he appropriat e
composit ion.
Fi gur e 8. 7
8- 8 St r eam Pr oper t y Vi ew
8- 8
BI P Opt i mi zer 9- 1
9- 1
9 BI P Opt imizer
9.1 I nt r oduct i on ............. ........................................................... .......... 2
9.2 BI P Opt i mi zer Vi ew ... ........................................................... .......... 2
9.3 Var i abl es Tab ............ ........................................................... .......... 3
9.4 Funct i ons Tab ........... ........................................................... .......... 4
9.5 Par amet er s Tab ........ ........................................................... .......... 5
9.6 Moni t or Tab .............. ........................................................... .......... 7
9.7 BI P Opt i mi zer Ti ps .... ........................................................... .......... 8
9.8 Ref er ences................ ........................................................... .......... 9
9- 2
UniSim Design cont ains a mult i- variable binary int eract ion paramet er
Opt imizer. Once your flow sheet has been built and a converged
solut ion has been obt ained, you can use t he BI P Opt imizer t o find t he
opt imal BI P' s of t he propert y package which minimize a Process
Obj ect ive Funct ion. The obj ect orient ed design of UniSim Design makes
t he BI P Opt imizer ext remely powerful, since it has access t o a wide
range of pr ocess variables for your opt imizat ion st udy.
9. 2 BI P Opt imizer View
To open t he BI P Opt imizer, select t he BI P Opt imizer command fr om t he
Simulat ion menu, or pr ess F6.
The BI P Opt imizer view cont ains t he following t abs:
Variable
Funct ions
Paramet ers
Monit or
When you first open t he BI P Opt imizer, t he figure below appears.
The BI P Opt i mi zer i s avai l abl e f or st eady st at e f l ow sheet
cal cul at i ons onl y. The oper at i on does not r un i n Dynami c
mode.
Fi gur e 9. 1
9- 3
Three but t ons are available on t he BI P Opt imizer view, no mat t er which
t ab is being viewed, or which mode of Opt imizer has been select ed.
9. 3 Variables Tab
When you invoke t he BI P Opt imizer for t he first t ime, t he Variables t ab
appears as shown in Fi gur e 9.1.
On t he Variables t ab, you can import t he BI P variables which minimize
or maximize t he obj ect ive funct ion. Any BI P variable which is not
specially t r eat ed under legacy t reat ment can be used as a pr imary
variable. New variables are added via t he BI P Variable Navigat or. The
five but t ons at t he bot t om of t he t able allow you t o manipulat e t he
variables.
All variables must be given upper and lower bounds, which are used t o
nor malize t he Primary Variable:
The upper and lower bound for each Primary Var iable should be chosen
such t hat a reasonable flowsheet solut ion is obt ained wit hin t he ent ire
range. I n case user does not configure t he lower and upper bound,
Delet e Erases all t he current informat ion from t he BI P
Opt imizer and it s spreadsheet .
Spreadsheet Accesses t he BI P Opt imizer s dedicat ed
Spreadsheet .
St art / St op St art s or st ops t he BI P Opt imizer calculat ions. An
obj ect ive funct ion must be defined prior t o t he
st art of t he calculat ions.
Add Allows you t o add t he BI P primary variables. When you click
t his but t on t he BI P Variable Navigat or view appears, and
you can select t he variable you want from t he list on t he
view.
Edit Allows you t o edit t he select ed primary variables for t he
variable you want t o change.
Delet e Allows you t o t he remove t he select ed variable.
Save Current St ores t he current value as t he Reset value.
Reset Current Reset s current values t o t he Reset value.
Reset Default Reset s current values t o t he package default value.
( 9. 1)
Refer t oSect i on - BI P
( Bi nar y I nt er act i on
Par amet er ) Par amet er
for more informat ion on
component pairs t reat ed
specifically under legacy
t reat ment .
low high
low
norm
x x
x x
x
=
9- 4 Funct i ons Tab
9- 4
UniSim Design t ries set t ing t hem wit hin 20% of t he cur rent value.
9. 4 Funct ions Tab
The Funct ions t ab cont ains t wo fields, t wo radio but t ons and t he
Const raint s Funct ions group.
The BI P Opt imizer possesses a dedicat ed Spreadsheet which is used t o
develop t he Obj ect ive funct ion, as well as any Const raint funct ions t o be
used.
For informat ion on using t he Spreadsheet , refer t o UniSim Design
Operat ions Guide Sect i on 12.10 - Spr eadsheet .
The BI P Opt imizer' s Spreadsheet is ident ical t o t he Spreadsheet
operat ion; process variables can be at t ached by dragging and dropping,
or using t he Variable Navigat or. Once t he necessary process variables
are connect ed t o t he Spreadsheet , you can const r uct t he Obj ect ive
Funct ion and any const raint s using t he st andard synt ax.
You can specify t he Obj ect ive Funct ion in t he Cell field. The current
value of t he obj ect ive funct ion is provided in t he display field below t he
Cell field. Furt her, t he obj ect ive funct ion group is t he locat ion where you
can specify ( via radio but t ons) t o minimize or maximize t he obj ect ive
Fi gur e 9. 2
To open t he Opt i mi zer Spr eadsheet , cl i ck t he Spr eadSheet
but t on.
9- 5
funct ion.
The Const raint Funct ions group is where you can specify t he left and
right sides of t he Const raint funct ion ( in t he LHS Cell and RHS Cell
columns) . Specify t he relat ionship bet ween t he left hand and right hand
cell ( LHS > RHS, LHS < RHS, LHS = RHS) in t he Cond column. The
Const raint Funct ion is mult iplied by t he Penalt y Value in t he
Opt imizat ion calculat ions. I f you find t hat a const raint is not being met ,
increase t he Penalt y Value; t he higher t he Penalt y Value, t he more
weight t hat is given t o t hat const raint . The Penalt y Value is equal t o 1
by default .
The current values of t he Obj ect ive Funct ion and t he left and right sides
of t he Const raint Funct ion cells appear in t heir respect ive fields.
9. 5 Paramet ers Tab
The Paramet ers t ab is used for select ing t he Opt imizat ion Scheme and
defining associat ed paramet ers.
The BOX, Mi x ed, and SQP Met hods al l ow f or I nequal i t y
Const r ai nt s. Onl y t he SQP Met hod i ncor por at es Equal i t y
Const r ai nt s.
Fi gur e 9. 3
9- 6 Par amet er s Tab
9- 6
The following t able cont ains a descript ion of each paramet er available.
Par amet er s Descr i pt i on
Scheme You can select t he scheme t ype from t he drop- down list .
Maximum Funct ion
Evaluat ion
Set s t he maximum number of funct ion evaluat ions ( not t o
be confused wit h t he maximum number of it erat ions) .
During each it erat ion, t he relevant port ion of t he flowsheet
is solved several t imes, depending on fact ors such as t he
Opt imizat ion Scheme, and number of primary variables.
Primary Variables are normalized.
Tolerance UniSim Design det ermines t he change in t he obj ect ive
funct ion bet ween it erat ions, as well as t he changes in t he
normalized primary variables. Using t his informat ion,
UniSim Design det ermines if t he specified t olerance is met .
Maximum I t erat ion The maximum number of it erat ions. Calculat ions st op if t he
maximum number of it erat ions is reached. All of t he
met hods except t he BOX met hod use derivat ives.
Maximum Change/
I t erat ion
The maximum allowable change in t he normalized primary
variables bet ween it erat ions. For inst ance, assume t he
maximum change per it erat ion is 0. 3 ( t his is t he default
value) . I f you have specified molar flow as a primary
variable wit h range 0 t o 200 kgmole/ hr, t hen t he maximum
change in one it erat ion would be ( 200) ( 0. 3) or 60 kgmole/
hr. Shift B ensures t hat t he Shift int erval xShift never be
zero.
low high
low
norm
x x
x x
x
=
9- 7
9. 6 Monit or Tab
The Monit or t ab displays t he values of t he obj ect ive funct ion, primary
variables, and const raint funct ions during t he Opt imizer calculat ions.
New informat ion is updat ed only when t here is an improvement in t he
value of t he Obj ect ive Funct ion. The const raint values ar e posit ive if
inequalit y const raint s are sat isfied and negat ive if inequalit y const raint s
Shift A/ Shift B Derivat ives of t he obj ect ive funct ion and/ or const raint
funct ions wit h respect t o t he primary variables are
generally required and are calculat ed using numerical
different iat ion. The numerical derivat ive is calculat ed from
t he following relat ionship:
where: x = pert urbed variable ( normalized)
xshift = shift int erval ( normalized) Derivat ives are
calculat ed using:
where: y2 = value of t he affect ed variable corresponding t o
x + xshift y1 = value of t he affect ed variable corresponding
t o x.
Prior t o each st ep, t he Opt imizer needs t o det ermine t he
gradient of t he opt imizat ion surface at t he current locat ion.
The Opt imizer moves each primary variable by a value of
xshift ( which due t o t he size of Shift A and Shift B be a very
small st ep) . The derivat ive is t hen evaluat ed for every
funct ion ( Obj ect ive and Const raint ) using t he values for y
at t he t wo locat ions of x. From t his informat ion and t he
Opt imizer hist ory, t he next st ep direct ion and size are
chosen. I n general, it should not be necessary t o change
Shift A and Shift B from t heir default s. Some Schemes
move all Primary variables simult aneously, while ot hers
move t hem sequent ially.
To det ermine each derivat ive, a variable evaluat ion must be
made in addit ion t o t he main flowsheet evaluat ion which is
done aft er each it erat ion ( main st ep change) . Therefore, if
t here are t wo primary variables, t here are t hree funct ion
evaluat ions for every it erat ion. I f you have select ed t he
Mixed Opt imizer Scheme, t he BOX and SQP met hods are
used in sequence - t his is t he reason why t he Funct ion
Evaluat ions are reset part way t hrough t he calculat ions.
Par amet er s Descr i pt i on
ShiftB x ShiftA x
shift
+ - =
Shift
x
y y
x
y
1 2

=
c
c
Refer t o UniSim Design
Operat ions Guide
Sect i on 13.2.5 -
Opt i mi zat i on Schemes
for more informat ion
about t he schemes.
9- 8 BI P Opt i mi zer Ti ps
9- 8
are not sat isfied.
9. 7 BI P Opt imizer Tips
The following are set up t ips for t he BI P Opt imizer.
1. BI P opt imizer uses ' Original Opt imizer' of UniSim Design Opt imizer
suit e. To overcome few limit at ions wit h t he opt imizer solver, cert ain
basic t ricks could be t ried out while facing any issues
Use square of t he residual error inst ead of absolut e residual
error as obj ect ive funct ion, even for obj ect ive funct ion value < 1
Scale- up t he obj ect ive funct ion value by mult iplying wit h bigger
number if t he value is found very less during st art of
opt imizat ion.
2. Reasonable upper and lower var iable bounds are ext remely
import ant . This is necessary not only t o prevent bad flowsheet
condit ions, but also because variables are scaled bet ween zero and
one in t he opt imizat ion algorit hms using t hese bounds.
3. For t he BOX and Mi x ed met hods, t he Maximum Change/ I t erat ion
of t he primary variables ( set on t he Par amet er s t ab) should be
reduced. A value of 0. 05 or 0. 1 is more appropriat e.
4. The Mi x ed met hod generally requires t he least number of funct ion
evaluat ions ( in ot her words, is t he most efficient ) .
5. I f t he BOX, Mi x ed or SQP Met hods are not honouring your
const raint s, t ry increasing t he Penalt y Value on t he Funct i ons t ab
by 3 or 6 orders of magnit ude ( up t o a value similar t o t he expect ed
value of t he obj ect ive funct ion) . I n ot her words, it is helpful t o
at t empt t o get t he magnit ude of t he obj ect ive funct ion and penalt y
as similar as possible ( especially when t he BOX Met hod is used) .
Fi gur e 9. 4
9- 9
6. By default t he BI P Opt imizer minimizes t he obj ect ive funct ion. You
can maximize t he obj ect ive funct ion by select ing t he Max i mi ze
radio but t on on t he Funct i ons t ab.
9. 8 References
1
Box, M. J. "A New met hod of Const rained Opt imizat ion and a Comparison wit h
ot her Met hods, " Comput er J., 8, 42- 45, 1965.
2
Press, W.H., et al, "Numerical Recipes in C, " Cambridge universit y Press,
1988.
9- 10 Ref er ences
9- 10
Pr oper t y Met hods & Cal cul at i ons A- 1
A- 1
A Propert y Met hods &
Calculat ions
A.1 I nt r oduct i on ............. ........................................................... .......... 3
A.2 Sel ect i ng Pr oper t y Met hods ................................................. .......... 4
A.3 Pr oper t y Met hods ..... ........................................................... .......... 8
A.3.1 Equat ions of St at e .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
A.3.2 Act ivit y Models .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 20
A.3.3 Act ivit y Model Vapour Phase Opt ions . .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 37
A.3.4 Semi- Empirical Met hods.. .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 40
A.3.5 Vapour Pressure Propert y Packages ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 41
A.3.6 Miscellaneous - Special Applicat ion Met hods ... .. ... .. .. ... .. ... .. .. ... .. .. 44
A.4 Ent hal py & Ent r opy Depar t ur e Cal cul at i ons ......................... .........46
A.4.1 Equat ions of St at e .. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 46
A.4.2 Act ivit y Models .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 48
A.4.3 Lee- Kesler Opt ion ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 50
A.5 Physi cal & Tr anspor t Pr oper t i es .......................................... .........52
A.5.1 Liquid Densit y ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 53
A.5.2 Vapour Densit y .. .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 53
A.5.3 Viscosit y . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 54
A.5.4 Liquid Phase Mixing Rules for Viscosit y. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 55
A.5.5 Thermal Conduct ivit y .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 56
A.5.6 Surface Tension . .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 59
A.5.7 Heat Capacit y . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 60
A.6 Vol umet r i c Fl ow Rat e Cal cul at i ons....................................... .........60
A.6.1 Available Flow Rat es.. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 61
A.6.2 Liquid & Vapour Densit y Basis. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 61
A.6.3 Formulat ion of Flow Rat e Calculat ions .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 63
A.6.4 Volumet ric Flow Rat es as Specificat ions . ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 65
A- 2 Pr oper t y Met hods & Cal cul at i ons
A- 2
A.7 Fl ash Cal cul at i ons..... ........................................................... .........65
A.7.1 T- P Flash Calculat ion . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 66
A.7.2 Vapour Fract ion Flash .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 67
A.7.3 Ent halpy Flash... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 68
A.7.4 Ent ropy Flash . ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 68
A.7.5 Elect rolyt e Flash .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 69
A.7.6 Handling of Wat er ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 70
A.7.7 Supercrit ical Handling.. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 71
A.7.8 Solids... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 72
A.7.9 St ream I nformat ion. .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 73
A.8 Ref er ences ............... ........................................................... .........75
A- 3
A. 1 I nt roduct ion
This appendix is organized such t hat t he det ailed calculat ions t hat occur
wit hin t he Simulat ion Basis Manager and wit hin t he Flowsheet are
explained in a logical manner.
I n t he first sect ion, an over view of propert y met hod select ion is
present ed. Various process syst ems and t heir recommended
propert y met hods are list ed.
Det ailed informat ion is provided concerning each individual
propert y met hod available in UniSim Design. This sect ion is
furt her subdivided int o equat ions of st at e, act ivit y models,
Chao- Seader based semi- empirical met hods, vapour pressure
models, and miscellaneous met hods.
Following t he det ailed pr opert y met hod discussion is t he sect ion
concerning ent halpy and ent ropy depart ure calculat ions. The
ent halpy and ent ropy opt ions available wit hin UniSim Design are
largely dependent upon your choice of a propert y met hod.
The physical and t ransport propert ies are covered in det ail. The
met hods used by UniSim Design in calculat ing liquid densit y,
vapour densit y, viscosit y, t hermal conduct ivit y, and surface
t ension are list ed.
UniSim Design handles volume flow calculat ions in a unique
way. To highlight t he met hods involved in calculat ing volumes, a
separat e sect ion is provided.
The next sect ion t ies all of t he previous informat ion t oget her.
Wit hin UniSim Design, t he Flash calculat ion uses t he equat ions
of t he select ed propert y met hod, as well as t he physical and
t ransport propert y funct ions t o det ermine all propert y values for
Flowsheet st reams. Aft er a flash calculat ion is performed on an
obj ect , all of it s t hermodynamic, physical and t ranspor t
propert ies are defined. The flash calculat ion in UniSim Design
does not require init ial guesses or t he specificat ion of flash t ype
t o assist in it s convergence.
A list of References is included at t he end of t he Appendix.
A- 4 Sel ect i ng Pr oper t y Met hods
A- 4
A. 2 Select ing Propert y
Met hods
The propert y packages available in UniSim Design allow you t o predict
propert ies of mixt ures ranging from well defined light hydr ocarbon
syst ems t o complex oil mixt ures and highly non- ideal ( non- elect rolyt e)
chemical syst ems. UniSim Design pr ovides enhanced equat ions of st at e
( PR and PRSV) for rigorous t reat ment of hydrocarbon syst ems; semi-
empirical and vapour pressure models for t he heavier hydr ocarbon
syst ems; st eam correlat ions for accurat e st eam propert y predict ions;
and act ivit y coefficient models for chemical syst ems. All of t hese
equat ions have t heir own inherent limit at ions and you are encouraged
t o become more familiar wit h t he applicat ion of each equat ion.
The following t able list s some t ypical syst ems and recommended
correlat ions. However, when in doubt of t he accuracy or applicat ion of
one of t he propert y packages, cont act Honeywell t o receive addit ional
validat ion mat erial or our best est imat e of it s accuracy.
For oil, gas and pet rochemical applicat ions, t he Peng- Robinson EOS
( PR) is generally t he recommended proper t y package. Honeywell' s
Ty pe of Syst em Recommended Pr oper t y Met hod
TEG Dehydrat ion PR
Sour Wat er Sour PR
Not e: The user is advised t o ensure
t hat Lee- Kesler opt ion for ent halpy
should be select ed since t he default
is EOS for Sour PR EOS
Cryogenic Gas Processing PR, PRSV
Air Separat ion PR, PRSV
At m Crude Towers PR, PR Opt ions, GS
Vacuum Towers PR, PR Opt ions, GS ( < 10 mm Hg) ,
Braun K10, Esso K
Et hylene Towers Lee Kesler Plocker
High H2 Syst ems PR, ZJ or GS ( see T/ P limit s)
Reservoir Syst ems PR, PR Opt ions
St eam Syst ems St eam Package, CS or GS
Hydrat e I nhibit ion PR
Chemical syst ems Act ivit y Models, PRSV
HF Alkylat ion PRSV, NRTL ( Cont act Honeywell)
TEG Dehydrat ion wit h Aromat ics PR ( Cont act Honeywell)
Hydrocarbon syst ems where H2O
solubilit y in HC is import ant
Kabadi Danner
Syst ems wit h select gases and light
hydrocarbons
MBWR
A- 5
enhancement s t o t his equat ion of st at e enable it t o be accurat e for a
variet y of syst ems over a wide range of condit ions. I t rigorously solves
any single, t wo- phase or t hree- phase syst em wit h a high degree of
efficiency and reliabilit y, and is applicable over a wide range of
condit ions, as shown in t he following t able.
The PR equat ion of st at e is enhanced t o yield accurat e phase
equilibrium calculat ions for syst ems ranging from low t emperat ure
cryogenic syst ems t o high t emperat ure, high pr essure reservoir
syst ems. The same equat ion of st at e sat isfact orily predict s component
dist ribut ions for heavy oil, aqueous glycol, and CH3OH syst ems.
Our high recommendat ion for t he PR equat ion of st at e is largely due t o
t he pr eferent ial at t ent ion t hat is given t o it by Honeywell. Alt hough t he
Soave- Redlich- Kwong ( SRK) equat ion also provides comparable result s
t o t he PR in many cases, it is known t hat it s range of applicat ion is
significant ly limit ed and it is not as reliable for non- ideal syst ems. For
example, it should not be used for syst ems wit h CH
3
OH or glycols.
As an alt ernat e, t he PRSV equat ion of st at e should also be considered.
I t can handle t he same syst ems as t he PR equat ion wit h equivalent , or
bet t er accuracy, plus it is more suit able for handling moderat ely non-
ideal syst ems.
The advant age of t he PRSV equat ion is t hat not only does it have t he
pot ent ial t o mor e accurat ely pr edict t he phase behaviour of
hydrocarbon syst ems, part icularly for syst ems composed of dissimilar
component s, but it can also be ext ended t o handle non- ideal syst ems
wit h accuracies t hat rival t radit ional act ivit y coefficient models. The
only compromise is increased comput at ional t ime and t he addit ional
int eract ion paramet er t hat is requir ed for t he equat ion.
The PR and PRSV equat ions of st at e perform rigor ous t hree- phase flash
calculat ions for aqueous syst ems cont aining H
2
O, CH
3
OH or glycols, as
well as syst ems cont aining ot her hydrocarbons or non- hydrocarbons in
t he second liquid phase. For SRK, H
2
O is t he only component t hat
init iat es an aqueous phase. The Chao- Seader ( CS) and Grayson- St r eed
( GS) packages can also be used for t hree- phase flashes, but are
rest rict ed t o t he use of pure H
2
O for t he second liquid phase.
The PR can also be used for crude syst ems, which have t radit ionally
been modeled wit h dual model t hermodynamic packages ( an act ivit y
model represent ing t he liquid phase behaviour, and an equat ion of st at e
Met hod Temp ( F) Temp ( C) Pr essur e ( psi a) Pr essur e ( k Pa)
PR > - 456 > - 271 < 15, 000 < 100, 000
SRK > - 225 > - 143 < 5,000 < 35, 000
The range of applicabilit y
in many cases is more
indicat ive of t he
availabilit y of good dat a
rat her t han on t he act ual
limit at ions.
A- 6 Sel ect i ng Pr oper t y Met hods
A- 6
or t he ideal gas law for t he vapour phase propert ies) . These earlier
models are suspect for syst ems wit h large amount s of light ends or
when appr oaching crit ical regions. Also, t he dual model syst em leads t o
int ernal inconsist encies. The pr opriet ary enhancement s t o t he PR and
SRK met hods allow t hese EOSs t o correct ly represent vacuum
condit ions and heavy component s ( a problem wit h t radit ional EOS
met hods) , as well as handle t he light ends and high- pressure syst ems.
Act ivit y Models, which handle highly non- ideal syst ems, are much more
empirical in nat ure when compared t o t he propert y predict ions in t he
hydrocarbon indust ry. Polar or non- ideal chemical syst ems are
t radit ionally handled using dual model appr oaches. I n t his t ype of
approach, an equat ion of st at e is used for predict ing t he vapour
fugacit y coefficient s and an act ivit y coefficient model is used for t he
liquid phase. Since t he experiment al dat a for act ivit y model paramet ers
are fit t ed for a specific range, t hese pr opert y met hods cannot be used
as reliably for generalized applicat ion.
The CS and GS met hods, t hough limit ed in scope, may be preferred in
some inst ances. For example, t hey are recommended for problems
cont aining mainly liquid or vapour H
2
O because t hey include special
correlat ions t hat accurat ely represent t he st eam t ables. The Chao
Seader met hod can be used for light hydrocar bon mixt ures, if desired.
The Grayson- St r eed cor relat ion is recommended for use wit h syst ems
having a high concent rat ion of H
2
because of t he special t reat ment
given H
2
in t he development of t he model. This correlat ion may also be
slight ly more accurat e in t he simulat ion of vacuum t owers.
The Vapour Pressure K models, Ant oine, BraunK10 and EssoK models,
are designed t o handle heavier hydrocarbon syst ems at lower
pressures. These equat ions are t radit ionally applied for heavier
hydrocarbon fract ionat ion syst ems and consequent ly provide a good
means of comparison against r igorous models. They should not be
considered for VLE pr edict ions for syst ems operat ing at high pressures
or syst ems wit h significant quant it ies of light hydrocarbons.
The Propert y Package met hods in UniSim Design are divided int o basic
cat egories, as shown in t he following t able. Wit h each of t he propert y
met hods list ed are t he available met hods of VLE and Ent halpy/ Ent ropy
calculat ion.
Pr oper t y Met hod VLE Cal cul at i on
Ent hal py / Ent r opy
Cal cul at i on
Equat i ons of St at e
PR PR PR
PR LK ENTH PR Lee- Kesler
SRK SRK SRK
Please refer t o Sect i on
A. 4 - Ent hal py &
Ent r opy Depar t ur e
Cal cul at i ons, for a
descript ion of Ent halpy
and Ent ropy calculat ions.
A- 7
SRK LK ENTH SRK Lee- Kesler
Kabadi Danner Kabadi Danner SRK
Lee Kesler Plocker Lee Kesler Plocker Lee Kesler
PRSV PRSV PRSV
PRSV LK PRSV Lee- Kesler
Sour PR PR & API - Sour PR, Lee- Kesler
Sour SRK SRK & API - Sour SRK
Zudkevit ch-Joffee Zudkevit ch-Joffee Lee- Kesler
Act i v i t y Model s
Li qui d
Chien Null Chien Null Cavet t
Ext ended and General
NRTL
NRTL Cavet t
Margules Margules Cavet t
NRTL NRTL Cavet t
UNI QUAC UNI QUAC Cavet t
van Laar van Laar Cavet t
Wilson Wilson Cavet t
Vapour
I deal Gas I deal I deal Gas
RK RK RK
Peng Robinson Peng Robinson Peng Robinson
SRK SRK SRK
Semi - Empi r i cal Model s
Chao- Seader CS- RK Lee- Kesler
Grayson- St reed GS- RK Lee- Kesler
Vapour Pr essur e Model s
Mod Ant oine Mod Ant oine- I deal Gas Lee- Kesler
Braun K10 Braun K10- I deal Gas Lee- Kesler
Esso K Esso- I deal Gas Lee- Kesler
Mi scel l aneous - Speci al Appl i cat i on Met hods
Amines Mod Kent Eisenberg
( L) , PR ( V)
Curve Fit
St eam Pack ages
ASME St eam ASME St eam Tables ASME St eam Tables
NBS St eam NBS/ NRC St eam Tables NBS/ NRC St eam Tables
MBWR Modified BWR Modified BWR
Pr oper t y Met hod VLE Cal cul at i on
Ent hal py / Ent r opy
Cal cul at i on
A- 8 Pr oper t y Met hods
A- 8
A. 3 Propert y Met hods
Det ails of each individual propert y met hod available in UniSim Design
are provided in t his sect ion, including equat ions of st at e, act ivit y
models, Chao- Seader based empirical met hods, vapour pressure
models, and miscellaneous met hods.
A. 3. 1 Equat ions of St at e
UniSim Design current ly offers t he enhanced Peng- Robinson
1
( PR) ,
Soave- Redlich- Kwong
2
( SRK) , modified Benedict - Webb- Rubin ( MBWR)
equat ions of st at e and Benedict - Webb- Rubin- St arling
24
,
25

and

26
( BWRS) .
I n addit ion, UniSim Design offers several met hods which are
modificat ions of t hese propert y packages, including PRSV, Zudkevit ch
Joffee ( ZJ) and Kabadi Danner ( KD) . Lee Kesler Plocker
3
( LKP) is an
adapt at ion of t he Lee Kesler equat ion for mixt ures, which it self was
modified from t he BWR equat ion. Of t hese, t he Peng- Robinson equat ion
of st at e support s t he widest range of operat ing condit ions and t he
great est variet y of syst ems. The Peng- Robinson and Soave- Redlich-
Kwong equat ions of st at e ( EOS) generat e all requir ed equilibr ium and
t hermodynamic pr opert ies direct ly. Alt hough t he forms of t hese EOS
met hods are common wit h ot her commercial simulat ors, t hey have
been significant ly enhanced by Honeywell t o ext end t heir range of
applicabilit y.
The Peng- Robinson propert y package opt ions are PR, Sour PR, and
PRSV. Soave- Redlich- Kwong equat ion of st at e opt ions are t he SRK,
Sour SRK, KD and ZJ.
PR & SRK
The PR and SRK packages cont ain enhanced binary int eract ion
paramet ers for all library hydr ocarbon- hydrocarbon pairs ( a
combinat ion of fit t ed and generat ed int eract ion paramet ers) , as well as
for most hydrocarbon- nonhydrocarbon binaries.
For non- library or hydrocarbon hypocomponent , HC- HC int eract ion
paramet ers are generat ed aut omat ically by UniSim Design for improved
VLE propert y predict ions.
The propert ies predict ed
by UniSim Designs' PR and
SRK equat ions of st at e do
not necessarily agree wit h
t hose predict ed by t he PR
and SRK of ot her
commercial simulat ors.
A- 9
The PR equat ion of st at e applies a funct ionalit y t o some specific
component - component int eract ion paramet ers. Key component s
receiving special t reat ment include He, H
2
, N
2,
CO
2
, H
2
S, H
2
O, CH
3
OH,
EG, DEG, and TEG. For furt her informat ion on applicat ion of equat ions
of st at e for specific component s, cont act Honeywell.
The following page provides a comparison of t he formulat ions used in
UniSim Design for t he PR and SRK equat ions of st at e.
The PR or SRK EOS shoul d not be used f or non- i deal
chemi cal s such as al cohol s, aci ds or ot her component s. They
ar e mor e accur at el y handl ed by t he Act i vi t y Model s ( hi ghl y
non- i deal ) or t he PRSV EOS ( moder at el y non- i deal ) .
Refer t o Peng Robi nson
Opt i ons for a descript ion
of St andard and UniSim
Design Peng- Robinson
opt ions.
Soav e Redl i ch Kw ong Peng Robi nson

where:
b=

b
i
=
a=
a
i
=
a
ci
=
=

m
i
=

When an acent ric fact or > 0. 49 is present UniSim
Design uses following correct ed form:
P
RT
V b
---------
a
V V b + ( )
---------------- =
Z
3
Z
2
A B B
2
( )Z AB + 0 =
P
RT
V b
---------
a
V V b + ( ) b V b ( ) +
------------------------------------ =
Z
3
1 B ( ) Z
2
A 2B 3B
2
( )Z AB B
2
B
3
( ) + 0 =
x
i
b
i
i 1 =
N
x
i
b
i
i 1 =
N
0.08664
RT
ci
P
ci
-------- 0.077796
RT
ci
P
ci
--------
x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
( )
j 1 =
N
i 1 =
N
x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
( )
j 1 =
N
i 1 =
N
a
ci
o
i
a
ci
o
i
0.42747
RT
ci
( )
2
P
ci
------------- 0.457235
RT
ci
( )
2
P
ci
-------------
o
i
0.5
1 m
i
1 T
ri
0.5
( ) +
1 m
i
1 T
ri
0.5
( ) +
0.48 1.574e
i
0.176e
i
2
+
0.37464 1.54226e
i
0.26992e
i
2
+
0.379642 1.48503 0.164423 1.016666e
i
( )e
i
( )e
i
+
A- 10
Kabadi Danner
This KD
4
model is a modificat ion of t he original SRK equat ion of St at e,
enhanced t o improve t he vapour- liquid- liquid equilibria calculat ions for
H2O- hydrocarbon syst ems, par t icularly in t he dilut e regions.
The model is an improvement over previous at t empt s which were
limit ed in t he region of validit y. The modificat ion is based on an
asymmet r ic mixing rule, whereby t he int eract ion in t he wat er phase
( wit h it s st rong H
2
bonding) is calculat ed based on bot h t he int eract ion
bet ween t he hydrocarbons and t he H
2
O, and on t he pert urbat ion by
hydrocarbon on t he H
2
O- H
2
O int eract ion ( due t o it s st ruct ure) .
Lee Kesler Plcker Equat ion
The Lee Kesler Plcker equat ion is an accurat e general met hod for polar
subst ances and mixt ures since it gives accurat e result s for polar
subst ances such as wat er over a normal EOS met hod. Plcker et al.
3

applied t he Lee Kesler equat ion t o mixt ures, which it self was modified
from t he BWR equat ion.
The compressibilit y fact ors are det ermined as follows:
A=
B=
Soav e Redl i ch Kw ong Peng Robi nson
aP
RT ( )
2
----------
aP
RT ( )
2
----------
bP
RT
-----
bP
RT
-----
( A. 1)
( A. 2)
( A. 3)
The Lee Kesler Plcker
equat ion does not use t he
COSTALD correlat ion in
comput ing liquid densit y.
This may result in
differences when
comparing result s
bet ween equat ion of
st at es.
z z
o ( ) e
e
r ( )
------- z
r ( )
z
o ( )
( ) + =
z
pv
RT
-----
p
r
v
r
T
r
------- z T
r
v
r
A
k
, , ( ) = = =
z 1
B
v
r
---
C
v
r
2
---
D
v
r
5
---
C
4
T
r
3
v
r
2
-------- |

v
r
2
--- +

v
r
2
---- exp + + + + =
A- 11
where:
Mixing rules for pseudocr it ical propert ies are as follows:
Peng- Robinson St ryj ek-Vera
The Peng- Robinson St ryj ek-Vera ( PRSV) equat ion of st at e is a t wo- fold
modificat ion of t he PR equat ion of st at e t hat ext ends t he applicat ion of
t he original PR met hod for moderat ely non- ideal syst ems. I t is shown t o
mat ch vapour pressures curves of pure component s and mixt ures more
accurat ely t han t he PR met hod, especially at low vapour pr essures.
I t is successfully ext ended t o handle non- ideal syst ems giving result s
as good as t hose obt ained using excess Gibbs energy funct ions like t he
Wilson, NRTL or UNI QUAC equat ions.
One of t he proposed modificat ions t o t he PR equat ion of st at e by
St r yj ek and Vera was an expanded alpha, , t erm t hat became a
funct ion of acent ricit y and an empirical paramet er, , used for fit t ing
( A. 4)
v
r
p
c
v
RT
c
------- =
C c
1
c
2
T
r
---
c
3
T
r
2
---- + =
e
o ( )
0 =
B b
1
b
2
T
r
----
b
3
T
r
2
----
b
4
T
r
3
---- =
D d
1
d
2
T
r
---- =
e
r ( )
0.3978 =
T
cm
1
V
cm
q
-------
\ .
|
| |
x
i
x
j
v
c
ij
j
=
T
c
i j
T
c
i
T
c
j
( )
1 2
= T
c
ii
T
c
i
= T
c
jj
T
c
j
=
v
c
m
x
i
x
j
v
c
i j
j
=
v
c
ij
1
8
-- v
c
i
1 3
v
c
j
1 3
+ ( )
3
=
v
c
i
z
c
i
RT
c
i
p
c
i
------- = z
c
i
0.2905 0.085e
i
=
p
c
m
z
c
m
RT
c
m
v
c
m
-------- = z
c
m
0.2905 0.085e
m
=
e
m
x
i
e
i
i
=
o
k
i
A- 12
pure component vapour pressures.
where:
= charact erist ic pure component paramet er
= acent ric fact or
The adj ust able t erm allows for a much closer fit of t he pure
component vapour pr essure curves. This t erm is regressed against t he
pure component vapour pressure for all component s in UniSim Design'
library.
For hypocomponent t hat are generat ed t o represent oil fract ions,
UniSim Design aut omat ically r egresses t he t erm for each
hypocomponent against t he Lee- Kesler vapour pr essure curves. For
individual user- added hypot het ical component s, t erms can eit her be
ent ered or t hey are aut omat ically regr essed against t he Lee- Kesler,
Gomez-Thodos or Reidel correlat ions.
The second modificat ion consist s of a new set of mixing rules for
mixt ures. Convent ional mixing rules are used for t he volume and
energy paramet ers in mixt ures, but t he mixing rule for t he cr oss t erm,
a
ij
, is modified t o adopt a composit ion dependent form. Alt hough t wo
different mixing rules were proposed in t he original paper, UniSim
Design has incorporat ed only t he Mar gules expression for t he cross
t erm.
where:
Alt hough only a limit ed number of binary pairs are regressed for t his
equat ion, our limit ed experience suggest s t hat t he PRSV can be used t o
model moderat ely non- ideal syst ems such as H
2
O- alcohol syst ems,
some hydrocarbon- alcohol syst ems. You can also model hydrocarbon
syst ems wit h improved accuracy. Also, due t o PRSV' s bet t er vapour
pressure predict ions, improved heat of vaporizat ion predict ions should
( A. 5)
( A. 6)
o
i
1 k
i
1 T
r
0.5
( ) + | |
2
=
k
i
k
0i
k +
1i
1 T
r
i
0.5
+ ( ) 0.7 T
r
i
0.5
( ) =
k
0i
0.378893 1.4897153e
i
0.17131848e
i
2
0.0196554e
i
3
+ + =
k
1i
e
i
k
1i
k
1i
k
1i
I f k
ij
= k
j i
, t he mixing
rules reduce t o t he
st andard PR equat ion of
st at e.
a
ij
a
ii
a
jj
( )
0.5
1.0 x
i
k
ij
x
j
k
ji
( ) =
k
ij
k
ji
=
Different values can be
ent ered for each of t he
binary int eract ion
paramet ers.
A- 13
be expect ed.
Sour Wat er Opt ions
The Sour opt ion is available for bot h t he PR and SRK equat ions of st at e.
The Sour PR opt ion combines t he PR equat ion of st at e and Wilson' s
API - Sour Model for handling sour wat er syst ems, while Sour SRK
ut ilizes t he SRK equat ion of st at e wit h t he Wilson model.
The Sour opt ions use t he appropriat e equat ion of st at e for calculat ing
t he fugacit ies of t he vapour and liquid hydrocarbon phases as well as
t he ent halpy for all t hree phases. The K- values for t he aqueous phase
are calculat ed using Wilson' s API - Sour met hod. This opt ion uses
Wilson' s model t o account for t he ionizat ion of t he H
2
S, CO
2
and NH
3
in
t he aqueous wat er phase. The aqueous model employs a modificat ion
of Van Krevelen' s original model wit h many of t he key limit at ions
removed. More det ails of t he model are available in t he original API
publicat ion 955 t it led " A New Correlat ion of NH
3
, CO
2
, and H
2
S
Volat ilit y Dat a from Aqueous Sour Wat er Syst ems" .
The original model is applicable for t emperat ures bet ween 20C ( 68F)
and 140C ( 285F) , and pressures up t o 50 psi. Use of eit her t he PR or
SRK equat ion of st at e t o correct vapour phase non idealit ies ext ends
t his range, but due t o lack of experiment al dat a, exact ranges cannot
be specified. The accept able pressure ranges for UniSim Designs' model
vary depending upon t he concent rat ion of t he acid gases and H
2
O. The
met hod performs well when t he H
2
O part ial pressure is below 100 psi.
This opt ion may be applied t o sour wat er st rippers, hydrot reat er loops,
crude columns or any process cont aining hydrocarbons, acid gases and
H
2
O. I f t he aqueous phase is not present , t he met hod produces
ident ical result s t o t he EOS, ( PR or SRK depending on which opt ion you
have chosen) .
Zudkevit ch Joffee
The Zudkevit ch Joffee model is a modificat ion of t he Redlich Kwong
equat ion of st at e. This model is enhanced for bet t er predict ion of
vapour liquid equilibria for hydrocarbon syst ems, and syst ems
cont aining H
2
. The maj or advant age of t his model over t he previous
version of t he RK equat ion is t he improved capabilit y of predict ing pure
component equilibria, and t he simplificat ion of t he met hod for
det ermining t he required coefficient s for t he equat ion.
Ent halpy calculat ions for t his model are performed using t he Lee Kesler
model.
The flash calculat ion is
much slower t han t he
st andard EOS, because
t he met hod performs an
ion balance for each K-
value calculat ion, .
A- 14
MBWR
I n UniSim Design, a 32- t erm modified BWR equat ion of st at e is used.
The modified BWR may be writ t en in t he following form:
where:
F = exp ( - 0. 0056 r2)
The modified BWR is applicable only for t he following pure component s:
( A. 7)
X
1
=
2
T X
8
=
3
/ T X
15
=
6
/ T
2
X
22
=
5
F/ T
2
X
29
=
11
F/ T
3
X
2
=
2
T
1/ 2
X
9
=
3
/ T
2
X
16
=
7
/ T X
23
=
5
F/ T
4
X
30
=
13
F/ T
2
X
3
=
2
X
10
=
4
T X
17
=
8
/ T X
24
=
7
F/ T
2
X
31
=
13
F/ T
3
X
4
=
2
/ T X
11
=
4
X
18
=
8
/ T
2
X
25
=
7
F/ T
3
X
32
=
13
F/ T
4
X
5
=
2
/ T
2
X
12
=
4
/ T X
19
=
9
/ T2 X
26
=
9
F/ T
2
X
6
=
3
T X
13
=
5
X
20
=
3
F/ T2 X
27
=
9
F/ T
4
X
7
=
3
X
14
=
6
/ T X
21
=
3
F/ T3 X
28
=
11
F/ T
2
Component Temp ( K) Temp ( R) Max Pr ess ( MPa) Max Pr ess ( psi a)
Ar 84 - 400 151. 2 - 720 100 14,504
CH
4
91 - 600 163. 8 - 1,080 200 29,008
C
2
H
4
104 - 400 187. 2 - 720 40 5,802
C
2
H
6
90 - 600 162. - 1,080 70 10,153
C
3
H
8
85 - 600 153. - 1080 100 14,504
i- C
4
114 - 600 205. 2 - 1,080 35 5,076
n- C
4
135 - 500 243. - 900 70 10,153
CO 68 - 1, 000 122. 4 - 1,800 30 4,351
CO
2
217 - 1, 000 390. 6 - 1,800 100 14,504
D
2
29 - 423 52. 2 - 761. 4 320 46,412
H
2
14 - 400 25. 2 - 720 120 17,405
o- H
2
14 - 400 25. 2 - 720 120 17,405
p- H
2
14 - 400 25. 2 - 720 120 17,405
He 0.8 - 1,500 1.4 - 2, 700 200 29,008
N
2
63 - 1, 900 113. 4 - 3,420 1,000 145, 038
O
2
54 - 400 97. 2 - 720 120 17,405
Xe 161 - 1, 300 289. 8 - 2,340 100 14,504
P RT N
i
X
i
i 1 =
32
+ =
A- 15
BWRS
The Benedict - Webb- Rubin- St arling equat ion- of st at e is t he bases of t he
BWRS propert y met hod. I t is a modificat ion by Han and St arling of t he
virial equat ion of st at e for pure fluid by Benedict , Webb and Rubin.
Some t imes, we call it SH- BWR equat ion of st at e. This equat ion of st at e
can be used for hydrocarbon syst ems t hat include t he common light
gases, such as H2S, CO2 and N2.
The form of t he equat ion of st at e is:
where:
The user can al so sel ect t he check box as show n i n t he f i gur e
bel ow , t o t r eat nor mal hy dr ogen as a mi x t ur e of par a
hy dr ogen and or t ho hy dr ogen on t he Fl ui d Pack age
pr oper t y vi ew w hen nor mal hy dr ogen and at l east one of
par a hy dr ogen and/ or or t ho hy dr ogen i n t he st r eam.
Fi gur e A. 1
( A. 8)
( ) ( )
2 2
2
3
6
3 2
4
0
3
0
2
0
0 0
exp 1
m m
m
m
m m m
T
c
T
d
a
T
d
a bRT
T
E
T
D
T
C
A RT B RT P

o

+ + |
.
|
\
|
+ +
|
.
|
\
|
+ |
.
|
\
|
+ + =
=
i
i i
B x B
0 0
( )
ij j
i j
i j i
k A A x x A =
1
2
1
0
2
1
0 0
A- 16
I n t he mixing rules given above, A
0i
, B
0i
, C
0i
, D
0i
, E
0i
, a
i
, b
i
, c
i
, d
i
,
o
i
, and
i
, are pure component const ant s which can be input by t he
user. I f t he values of t hese paramet ers are not given, t he Physical
Propert y Syst em will calculat e t hem using t he crit ical t emperat ur e, t he
( )
3
2
1
0
2
1
0 0
1
ij j
i j
i j i
k C C x x C =
2
2
1
|
|
.
|
\
|
=

i
i i
x
b x
i
b
i
1
3
--
i
\ .
|
| |
3
=
3
3
1
|
|
.
|
\
|
=

i
i i
a x a
3
3
1
|
|
.
|
\
|
=

i
i i
x o o
3
3
1
|
|
.
|
\
|
=

i
i i
c x c
D
0
x
i
x
j
D
0i
1
2
--
D
0j
1
2
--
1 k
ij
( )
4
j
=
3
3
1
|
|
.
|
\
|
=

i
i i
d x d
( )
5
2
1
0
2
1
0 0
1
ij j
i j
i j i
k E E x x E =
ji ij
k k =
A- 17
crit ical volume ( or crit ical densit y) , t he acent ric fact or and generalized
correlat ions given by Han and St arling.
For best result s, t he binary paramet er must be regressed using phase-
equilibrium dat a such as VLE dat a.
PR-Twu, SRK-Twu, Twu- Sim-Tassone
( TST)
These Equat ions of St at e
27

28

29

30

31
are using Twu modified funct ion
which is present ed in t he general cubic equat ion of st at e form:
Where , which account s for t he at t ract ive cont ribut ion; b is
t he volume cont ribut ion. Twu' s funct ion has higher accuracy and is
capable of giving good ext rapolat ion t o heavy hydr ocarbons and
smoot h t ransit ion from subcrit ical t o supercrit ical region. TST equat ion
yields bet t er result s for vapor pressure and liquid densit y for high
number hydrocarbons, i. e. from n- oct ane and higher. The det ails about
funct ion and equat ion paramet ers are list ed in t he following t ables.
For a hypo compound cl oned f r om t he l i br ar y component , t he
v al ues of i t s BWRS par amet er s ar e copi ed f r om t he pur e
component i f t he cl one happens af t er t he BWRS f l ui d
pack age has been set up; ot her w i se t he par amet er s w i l l be
est i mat ed by t he gener al i zed cor r el at i ons.
( A. 9)
Par amet er s i n SRK- Tw u, PR- Tw u and TST CEOS
SRK- Tw u PR- Tw u TST
u, w u= 1. 0, w= o. o u= 2. 41421,
w= - 0. 41421
u= 3. 0,
w= - 0. 5
a
c
b
Z
c
0.3333 0.3074 0.296296
o
P
RT
V b
---------
a T ( )
V
2
ubV wb
2
+ +
---------------------------- =
a T ( ) o T ( )a
c
=
o
o
0.42747R
2
T
c
2
lP
c
0.457235R
2
T
c
2
lP
c
0.470507R
2
T
c
2
lP
c
0.08664RT
c
lP
c
0.077796RT
c
lP
c
0.074074RT
c
lP
c
A- 18
I n all t hese CEOSs, is given by t he r elat ion
Where . The paramet ers L, M and N depend on individual
compounds and can be ret rieved from UniSim Design library for most of
t hem. For non- library compounds, t hey can be est imat ed by
Where t he relevant paramet ers are list ed in t he following t ables 2- 4
(A.10)
(A.11)
(A.12)
(A.13)
Par amet er s i n SRK- Tw u equat i on
L 0.141599 0.500315 0.441411 0.032580
M 0.919422 0.799457 6.500018 1.289098
N 2.496441 3.29179 - 0. 20000 - 8. 00000
Par amet er s i n PR- Tw u equat i on
L 0.125283 0.511614 0.401219 0.024955
M 0.911807 0.784054 4.963070 1.248089
N 1.948150 2.81252 - 0. 20000 - 8. 00000
o T ( )
o T ( ) T
r
N M 1 ( )
e
L 1 T
r
MN
( )
=
T
r
T T
c
=
a T ( ) o
0 ( )
T ( ) e o
1 ( )
T ( ) o
0 ( )
T ( ) ( ) + =
o
0 ( )
T ( ) T
r
N
0 ( )
M
0 ( )
1 ( )
e
L
0 ( )
1 T
r
M
0 ( )
N
0 ( )
\ .
| |
=
o
1 ( )
T ( ) T
r
N
1 ( )
M
1 ( )
1 ( )
e
L
1 ( )
1 T
r
M
1 ( )
N
1 ( )
\ .
| |
=
T
r
1 s T
r
1 >
o
o
0 ( )
o
1 ( )
o
0 ( )
o
1 ( )
T
r
1 s T
r
1 >
o
o
0 ( )
o
1 ( )
o
0 ( )
o
1 ( )
A- 19
For mixt ures, t he paramet ers in t hese GCEOS are calculat ed by
convent ional mixing rules:
Where k
ij
is binary paramet er of at t ract ion bet ween compound i and j .
EOS Ent halpy Calculat ion
Wit h any t he Equat ion of St at e opt ions except ZJ, LKP and MBWR, you
can specify whet her t he Ent halpy is calculat ed by eit her t he Equat ion of
St at e met hod or t he Lee Kesler met hod. The ZJ and LKP propert y
packages must use t he Lee Kesler met hod in Ent halpy calculat ions.
Select ion of an ent halpy met hod is done by select ing radio but t ons in
t he Ent halpy Met hod group.
Select ing t he Lee Kesler Ent halpy opt ion result s in a combined propert y
package employing t he appropriat e equat ion of st at e ( eit her PR or SRK)
for vapour- liquid equilibrium calculat ions and t he Lee- Kesler equat ion
for calculat ion of ent halpies and ent ropies.
The LK met hod yields comparable result s t o UniSim Design' st andard
equat ions of st at e and has ident ical ranges of applicabilit y. As such, t his
opt ion wit h PR has a slight ly great er range of applicabilit y t han wit h
SRK.
Par amet er s i n Tw u- Si m- Tassone equat i on
L 0.196545 0.704001 0.358826 0.020644
M 0.906437 0.790407 4.23478 1.22942
N 1.26251 2.13086 - 0. 20000 - 8. 00000
(A.14)
Fi gur e A. 2
T
r
1 s T
r
1 >
o
o
0 ( )
o
1 ( )
o
0 ( )
o
1 ( )
a x
i
x
j
a
i
a
j
( )
1 2
1 k
ij
( ) b ,
j 1 =
N
i 1 =
N
x
i
b
i
i 1 =
N
= =
The Lee- Kesler
ent halpies may be
slight ly more accurat e
for heavy hydrocarbon
syst ems, but require
more comput er
resources because a
separat e model must be
solved.
For informat ion on t he
differences bet ween EOS
and LK met hods, refer t o
t he Sect i on A. 4 -
Ent hal py & Ent r opy
Depar t ur e
Cal cul at i ons.
A- 20
Zero Kij Opt ion
UniSim Design aut omat ically generat es hydrocarbon- hydrocarbon
int eract ion paramet ers when values are unknown if t he Est imat e HC-
HC/ Set Non HC- HC t o 0. 0 radio but t on is select ed. The Set All t o 0. 0
radio but t on t urns off t he aut omat ic calculat ion of any est imat ed
int eract ion coefficient s bet ween hydrocarbons. All binary int eract ion
paramet ers t hat are obt ained from t he pure component library remain.
The Set All t o 0. 0 opt ion may prove useful when t rying t o mat ch result s
from ot her commercial simulat ors which may not supply int eract ion
paramet ers for higher molecular weight hydrocarbons.
A. 3. 2 Act ivit y Models
Alt hough equat ion of st at e models have proven t o be reliable in
predict ing propert ies of most hydrocarbon based fluids over a large
non- polar or slight ly polar component s. Polar or non- ideal chemical
syst ems are t radit ionally handled using dual model approaches. I n t his
approach, an equat ion of st at e is used for predict ing t he vapour
fugacit y coefficient s ( normally ideal gas assumpt ion or t he Redlich
Kwong, Peng- Robinson or SRK equat ions of st at e, alt hough a Virial
equat ion of st at e is available for specific applicat ions) and an act ivit y
coefficient model is used for t he liquid phase. Alt hough t here is
considerable research being conduct ed t o ext end equat ion of st at e
applicat ions int o t he chemical arena ( e. g., t he PRSV equat ion) , t he
st at e of t he art of propert y predict ions for chemical syst ems is st ill
governed mainly by Act ivit y Models.
Act ivit y Models are much more empirical in nat ure when compared t o
t he propert y predict ions ( equat ions of st at e) t ypically used in t he
hydrocarbon indust ry. For example, t hey cannot be used as r eliably as
t he equat ions of st at e for generalized applicat ion or ext rapolat ing int o
unt est ed operat ing condit ions. Their t uning paramet ers should be fit t ed
against a represent at ive sample of experiment al dat a and t heir
applicat ion should be limit ed t o moderat e pressures. Consequent ly,
more caut ion should be exercised when select ing t hese models for your
simulat ion.
The phase separat ion or equilibrium rat io K
i
for component i, defined in
Fi gur e A. 3
This opt ion is set on t he
Binary Coeffs t ab of t he
Fluid Package propert y
view.
Act ivit y Models produce
t he best result s when
t hey are applied in t he
operat ing region for
which t he int eract ion
paramet ers were
regressed.
A- 21
t erms of t he vapour phase fugacit y coefficient and t he liquid phase
act ivit y coefficient is calculat ed fr om t he following expression:
where:
= liquid phase act ivit y coefficient of component i
f
i
= st andard st at e fugacit y of component i
P = syst em pressure
= vapour phase fugacit y coefficient of component i
Alt hough for ideal solut ions t he act ivit y coefficient is unit y, for most
chemical ( non- ideal) syst ems t his approximat ion is incorrect . Dissimilar
chemicals normally exhibit not only large deviat ions from an ideal
solut ion, but t he deviat ion is also found t o be a st rong funct ion of t he
composit ion. To account for t his non- idealit y, act ivit y models were
developed t o predict t he act ivit y coefficient s of t he component s in t he
liquid phase. The derived correlat ions were based on t he excess Gibbs
energy funct ion, which is defined as t he observed Gibbs ener gy of a
mixt ure in excess of what it would be if t he solut ion behaved ideally, at
t he same t emperat ure and pressure.
For a mult i- component mixt ure consist ing of n
i
moles of component i,
t he t ot al excess Gibbs free energy is represent ed by t he following
expression:
where:
= act ivit y coefficient for component i
The individual act ivit y coefficient s for any syst em can be obt ained from
a derived expression for excess Gibbs energy funct ion coupled wit h t he
Gibbs- Duhem equat ion. The early models ( Margules, van Laar) provide
an empirical represent at ion of t he excess funct ion t hat limit s t heir
applicat ion. The newer models such as Wilson, NRTL and UNI QUAC
ut ilize t he local composit ion concept and provide an improvement in
t heir general applicat ion and reliabilit y. All of t hese models involve t he
concept of binary int eract ion paramet ers and require t hat t hey be fit t ed
t o experiment al dat a.
(A.15)
(A.16)
K
i
y
i
x
i
--- =
i
f
i
P|
i
------- =
i
|
i
G
E
RT n
i

i
ln ( )
i
A- 22
Since t he Margules and van Laar models are less complex t han t he
Wilson, NRTL and UNI QUAC models, t hey require less CPU t ime for
solving flash calculat ions. However, t hese are older and more
empirically based models and generally give poor result s for st rongly
non- ideal mixt ures such as alcohol- hydrocarbon syst ems, part icularly
for dilut e r egions. The Chien- Null model provides t he abilit y t o
incorporat e t he different act ivit y models wit hin a consist ent
t hermodynamic framework. Each binary can be represent ed by t he
model which best predict s it s behaviour.
The following t able briefly summarizes recommended models for
different applicat ions ( for a more det ailed review, refer t o t he t ext s
The Proper t ies of Gases & Liquids
8
and Molecular Thermodynamics of
Fluid Phase Equilibria
9
) .
A = Applicable; N/A = Not Applicable;? = Questionable; G = Good; LA = Limited Application
Vapour phase non- idealit y can be t aken int o account for each act ivit y
model by select ing t he Redlich- Kwong, Peng- Robinson, or SRK
equat ions of st at e as t he vapour phase model. When one of t he
equat ions of st at e is used for t he vapour phase, t he st andard form of
t he Poynt ing correct ion fact or is always used for liquid phase correct ion.
I f dimerizat ion occurs in t he vapour phase, t he Virial equat ion of st at e
should be select ed as t he vapour phase model.
The binary paramet ers requir ed for t he act ivit y models are regressed
based on t he VLE dat a collect ed from DECHEMA, Chemist ry Dat a
Series
3
. There are over 16, 000 fit t ed binary pairs in t he UniSim Design
library. The st ruct ures of all library component s applicable for t he
UNI FAC VLE est imat ion are also in t he library. The Poynt ing correct ion
for t he liquid phase is ignored if ideal solut ion behaviour is assumed.
I f you are using t he built - in binary paramet ers, t he ideal gas model
should be used. All act ivit y models, wit h t he except ion of t he Wilson
equat ion, can aut omat ically calculat e t hree phases given t he corr ect set
of energy paramet ers. The vapour pressures used in t he calculat ion of
Appl i cat i on Mar gul es v an Laar Wi l son NRTL UNI QUAC
Binary Syst ems A A A A A
Mult icomponent
Syst ems
LA LA A A A
Azeot ropic Syst ems A A A A A
Liquid- Liquid Equilibria A A N/ A A A
Dilut e Syst ems ? ? A A A
Self-Associat ing
Syst ems
? ? A A A
Polymers N/ A N/ A N/ A N/ A A
Ext rapolat ion ? ? G G G
All of t he binary
paramet ers in t he
UniSim Design library
are regressed using an
ideal gas model for t he
vapour phase.
UniSim Design int ernally
st ored binary
paramet ers are NOT
regressed against t hree
phase equilibrium dat a.
A- 23
t he st andard st at e fugacit y are based on t he pure component
coefficient s in UniSim Design' library using t he modified form of t he
Ant oine equat ion.
When your select ed component s exhibit dimerizat ion in t he vapour
phase, t he Virial opt ion should be select ed as t he vapour phase model.
UniSim Design cont ains fit t ed paramet ers for many carboxylic acids,
and can est imat e values from pure component propert ies if t he
necessary paramet ers are not available.
General Remarks
The dual model approach for solving chemical syst ems wit h act ivit y
models cannot be used wit h t he same degree of flexibilit y and reliabilit y
t hat t he equat ions of st at e can be used for hydrocarbon syst ems.
However, some checks can be devised t o ensure a good confidence
level in propert y predict ions:
Check t he propert y package select ed for applicabilit y for t he
syst em considered and see how well it mat ches t he pure
component vapour pressures. Alt hough t he predict ed pure
component vapour pressures should normally be accept able, t he
paramet ers are fit t ed over a large t emperat ure range. I mpr oved
accuracies can be at t ained by regressing t he paramet ers over
t he desired t emperat ure range.
The aut omat ic UNI FAC generat ion of energy paramet ers in
UniSim Design is a very useful t ool and is available for all
act ivit y models. However, it must be used wit h caut ion. The
st andard fit t ed values in UniSim Design likely produce a bet t er
fit for t he binary syst em t han t he paramet ers generat ed by
UNI FAC. As a general rule, use t he UNI FAC generat ed
paramet ers only as a last resort .
Always use experiment al dat a t o regress t he energy paramet ers
when possible. The energy paramet ers in UniSim Design are
regressed fr om experiment al dat a, however, improved fit s are
st ill possible by fit t ing t he paramet ers for t he narrow operat ing
ranges ant icipat ed. The regr essed paramet ers are based on dat a
t aken at at mospheric pressures. Exercise caut ion when
ext rapolat ing t o higher or lower pressure ( vacuum) applicat ions.
Check t he accuracy of t he model for azeot r opic syst ems.
Addit ional fit t ing may be requir ed t o mat ch t he azeot rope wit h
accept able accuracy. Check not only for t he t emperat ure, but for
t he composit ion as well.
I f t hree phase behaviour is suspect ed, addit ional fit t ing of t he
paramet ers may be required t o reliably reproduce t he VLLE
equilibrium condit ions.
An impr ovement in mat ching equilibrium dat a can be at t ained
by including a t emperat ure dependency of t he energy
paramet ers. However, depending on t he validit y or range of fit ,
t his can lead t o misleading result s when ext rapolat ing beyond
t he fit t ed t emperat ure range.
By default , UniSim Design regresses ONLY t he a
ij
paramet ers while t he
Refer t o Sect i on A.3.3
- Act i v i t y Model
Vapour Phase Opt i ons
for a det ailed descript ion
of t he Virial opt ion.
The act ivit ies for t he
unknown binaries are
generat ed at pre- select ed
composit ions and t he
supplied UNI FAC
reference t emperat ure.
A- 24
b
ij
paramet ers are set t o zero, i. e., t he a
ij
t erm is assumed t o be
t emperat ure independent . A t emperat ure dependency can be
incorporat ed by supplying a value for t he b
ij
t erm. The mat rix for t he b
ij

values are displayed by select ing t he B
ij
radio but t on t o swit ch mat rices
( not e t he zero or blank ent ries for all t he binary pairs) .
When using t he NRTL, General NRTL or Ext ended NRTL equat ions, more
t han t wo mat rices are available. I n general, t he second mat rix is t he B
ij
mat rix, and t he t hird mat r ix is t he paramet er where . Any
component pair wit h an a
ij
value has an associat ed value.
I mmiscible
This opt ion is included for modeling t he solubilit y of solut es in t wo
coexist ing liquid phases t hat are relat ively immiscible wit h one anot her,
such as a H
2
O- hydrocarbon syst em. I n t his syst em, t he hydrocarbon
component s ( solut es) are relat ively insoluble in t he wat er phase
( solvent ) whereas t he solubilit y of t he H
2
O in t he hydrocarbon phase
can become more significant . The limit ed mut ual solubilit y behaviour
can be t aken int o account when using any act ivit y model wit h t he
except ion of Wilson.
This feat ure can be implement ed for any single component pair by
using t he I mmiscible radio but t on. Component i is insoluble wit h
component j , based on t he highlight ed cell locat ion. Alt ernat ively, you
can have all j component s t reat ed as insoluble wit h component i.
UniSim Design replaces t he st andard binary paramet ers wit h t hose
regressed specifically for mat ching t he solubilit ies of t he solut es in bot h
phases.
These paramet ers were regressed from t he mut ual solubilit y dat a of n-
C
5
, n- C
6
, n- C
7
, and n- C
8
in H
2
O over a t emperat ure range of 313 K t o
473 K.
The solubilit y of H
2
O in t he hydrocarbon phase and t he solubilit y of t he
hydrocarbons in t he wat er phase are calculat ed based on t he fit t ed
binary paramet ers regr essed from t he solubilit y dat a referenced above.
Chien- Null
Bot h t he a
i j
and b
i j
par amet er s ar e r egr essed w i t h t he
i mmi sci bl e opt i on.
o
ij
o
ij
o
ji
=
o
The Wilson equat ion does
not support LLE
equilibrium.
A- 25
exist ing act ivit y models on a binary by binary basis. I n t his manner, t he
Chien Null model allows you t o select t he best act ivit y model for each
pair in t he case.
The Chien Null model allows t hr ee set s of coefficient s for each
component pair, accessible t hrough t he A, B and C coefficient mat r ices.
Please refer t o t he following sect ions for an explanat ion of t he t erms for
each of t he models.
Chien Null Form
The Chien- Null generalized mult i- component equat ion can be
expressed as follows:
Each of t he paramet ers in t his equat ion ar e defined specifically for each
of t he applicable act ivit y met hods.
Descript ion of Terms
The Regular Solut ion equat ion uses t he following:
is t he solubilit y paramet er in ( cal/ cm
3
)
and v
i
L
is t he sat urat ed
liquid volume in cm
3
/ mol calculat ed from:
(A.17)
(A.18)
(A.19)
2 I
i
L
ln
A
j i ,
x
j
j
\ .
|
| |
R
j i ,
x
j
j
\ .
|
| |
S
j i ,
x
j
j
\ .
|
| |
V
j i ,
x
j
j
\ .
|
| |
----------------------------------------- x
k
A
j k ,
x
j
j
\ .
|
| |
R
j k ,
x
j
j
\ .
|
| |
S
j k ,
x
j
j
\ .
|
| |
V
j k ,
x
j
j
\ .
|
| |
---------------------------------------------
k
+ =
A
i k ,

A
j k ,
x
j
j
-----------------
R
i k ,

R
j k ,
x
j
j
-----------------
S
i k ,

S
j k ,
x
j
j
----------------
V
i k ,

V
j k ,
x
j
j
----------------- +
A
i j ,
v
i
L
o
i
o
j
( )
2
RT
-------------------- = R
i j ,
A
i j ,
A
j i ,
------ = V
i j ,
R
i j ,
= S
i j ,
R
i j ,
=
o
i
v
i
L
v
e i ,
5.7 3T
r i ,
+ ( ) =
A- 26
The van Laar, Margules and Scat chard Hamer use t he following:
For t he van Laar, Margules and Scat chard Hamer equat ions:
where:
T = t emperat ure unit must be in K
Model A
i ,j
R
i ,j
S
i , j
V
i , j
van Laar
Margules
Scat chard Hamer
(A.20)
The Equat i on ( A.20) i s of a di f f er ent f or m t han t he or i gi nal
van Laar and Mar gul es equat i ons i n Uni Si m Desi gn, w hi ch
uses an a + bT r el at i onshi p. How ever , si nce Uni Si m Desi gn
onl y cont ai ns a
i j
v al ues, t he di f f er ence shoul d not cause
pr obl ems.
I f y ou have r egr essed par amet er s usi ng HYPROP f or any of
t he Act i v i t y Model s suppor t ed under t he Chi en Nul l , t hey ar e
not r ead i n.
i j ,
ln
A
i j ,
A
j i ,
------
R
i j ,
R
i j ,
2
i j ,
ln
1

i j ,
ln
j i ,
ln
------------
\ .
|
| |
+
-----------------------
A
i j ,
A
j i ,
------
1 1
2
i j ,
ln
1

i j ,
ln
j i ,
ln
------------
\ .
|
| |
+
-----------------------
A
i j ,
A
j i ,
------
v
i
v
j
----
v
i
v
j
----
i j ,
ln a
i j ,
b
i j ,
T
----- c
ij
T + + =
A- 27
The NRTL form for t he Chien Null uses:
The expression for t he t erm under t he Chien Null incorporat es t he R
t erm of UniSim Design' NRTL int o t he values for a
ij
and b
ij
. As such, t he
values init ialized for NRTL under Chien Null are not t he same as for t he
regular NRTL. When you select NRTL for a binary pair, a
ij
is empt y
( essent ially equivalent t o t he regular NRTL b
ij
t erm) , b
ij
is init ialized
and c
ij
is t he t erm for t he original NRTL, and is assumed t o be
symmet ric.
The General Chien Null equat ion is:
I n all cases:
Wit h t he except ion of t he Regular Solut ion opt ion, all models can ut ilize
six const ant s, a
i, j
, a
j , i
, b
i, j
, b
j , i
, c
i, j
and c
j , i
for each component pair. For
all models, if t he const ant s are unknown t hey can be est imat ed
int ernally from t he UNI FAC VLE or LLE met hods, t he I nsoluble opt ion,
or using Henry' s Law coefficient s for appropriat e component s. For t he
general Chien Null model, t he c
ij
' s are assumed t o be 1.
Ext ended & General NRTL
The Ext ended and General NRTL models are variat ions of t he NRTL
model. More binary int eract ion paramet ers are used in defining t he
component act ivit y coefficient s. You may apply eit her model t o
syst ems:
wit h a wide boiling point range bet ween component s.
where you require simult aneous solut ion of VLE and LLE, and
t here exist s a wide boiling point range or concent rat ion range
bet ween component s.
You can specify t he format for t he Equat ions of

and a
ij
t o be any of
(A.21)
(A.22)
(A.23)
A
i j ,
2t
i j ,
V
i j ,
= R
i j ,
1 = V
i j ,
c
i j ,
t
i j ,
( ) exp = S
i j ,
1 = t
i j ,
a
i j ,
b
i j ,
T K ( )
--------- + =
t
o
A
i j ,
a
i j ,
b
i j ,
T K ( )
--------- + = R
i j ,
A
i j ,
A
j i ,
------ = V
i j ,
C
i j ,
= S
i j ,
C
i j ,
=
A
i i ,
0 = R
i i ,
S
i i ,
V
i i ,
1 = = =
t
ij
A- 28
t he following:
Depending on which form of t he equat ions t hat you have select ed, you
are able t o specify values for t he different component energy
paramet ers. The General NRTL model provides radio but t ons on t he
Binary Coeffs t ab which access t he mat rices for t he A
ij
, B
ij
, C
ij
, F
ij
, G
ij
,
Alp1
ij
and Alp2
ij
energy paramet ers.
Opt i ons
The equat ions opt ions
can be viewed in t he
Display Form drop- down
list on t he Binary Coeffs
t ab of t he Fluid Package
propert y view.
t
ij
and o
ij
t
ij
A
ij
B
ij
T
-----
C
ij
T
2
----- F
ij
T G
ij
T ( ) ln + + + + =
o
ij
Alp1
ij
Alp2
ij
T + =
t
ij
A
ij
B
ij
T
----- +
RT
-------------- =
o
ij
Alp1
ij
=
t
ij
A
ij
B
ij
T
----- F
ij
T G
ij
T ( ) ln + + + =
o
ij
Alp1
ij
Alp2
ij
T + =
t
ij
A
ij
B
ij
t
C
ij
T
----- + + =
o
ij
Alp1
ij
Alp2
ij
T + =
where: T is in K and t is C
t
ij
A
ij
B
ij
T
----- + =
o
ij
Alp1
ij
=
A- 29
The Ext ended NRTL model allows you t o input values for t he A
ij
, B
ij
, C
ij
,
Alp1
ij
and Alp2
ij
energy paramet ers by select ing t he appropriat e radio
but t on. You do not have a choice of equat ion format for . The
following is used:
where:
T = t emperat ure in K
t = t emperat ure in C
Margules
The Mar gules equat ion was t he first Gibbs excess energy
represent at ion developed. The equat ion does not have any t heoret ical
basis, but is useful for quick est imat es and dat a int erpolat ion. UniSim
Design has an ext ended mult icomponent Margules equat ion wit h up t o
four adj ust able paramet ers per binary.
The four adj ust able paramet ers for t he Margules equat ion in UniSim
Design are t he a
ij
and a
j i
( t emperat ure independent ) and t he b
ij
and b
ji

t erms ( t emperat ure dependent ) . The equat ion uses paramet er values
st ored in UniSim Design or any user supplied value for furt her fit t ing
t he equat ion t o a given set of dat a.
The Mar gules act ivit y coefficient model is represent ed by t he following
equat ion:
where:
= act ivit y coefficient of component i
x
i
= mole fract ion of component i
A
i
=
B
i
=
(A.24)
(A.25)
t
ij
and o
ij
t
ij
A
ij
B
ij
t
C
ij
T
----- + +
\ .
| |
=
o
ij
Alp1
ij
Alp2
ij
+ =
The equat ion should not
be used for ext rapolat ion
beyond t he range over
which t he energy
paramet ers are fit t ed.
i
ln 1.0 x
i
| |
2
A
i
2x
i
B
i
A
i
( ) + | | =
i
x
j
a
ij
b
ij
T + ( )
1.0 x
i
( )
--------------------
j 1 =
n
x
j
a
ji
b
ji
T + ( )
1.0 x
i
( )
--------------------
j 1 =
n

A- 30
T = t emperat ure ( K)
n = t ot al number of component s
a
ij
= non- t emperat ure dependent energy paramet er bet ween
component s i and j
b
ij
= t emperat ure dependent energy paramet er bet ween component s
i and j [ 1/ K]
a
j i
component s j and i
b
j i
j and i [ 1/ K]
NRTL
The NRTL ( Non- Random-Two- Liquid) equat ion, pr oposed by Renon and
Prausnit z in 1968, is an ext ension of t he original Wilson equat ion. I t
uses st at ist ical mechanics and t he liquid cell t heory t o represent t he
liquid st ruct ure. These concept s, combined wit h Wilson' s local
composit ion model, produce an equat ion capable of represent ing VLE,
LLE and VLLE phase behaviour.
Like t he Wilson equat ion, t he NRTL is t hermodynamically consist ent and
can be applied t o t ernary and higher order syst ems using paramet ers
regressed fr om binary equilibrium dat a. I t has an accuracy comparable
t o t he Wilson equat ion for VLE syst ems.
The NRTL equat ion in UniSim Design cont ains five adj ust able
paramet ers ( t emperat ure dependent and independent ) for fit t ing per
binary pair. The NRTL combines t he advant ages of t he Wilson and van
Laar equat ions, and, like t he van Laar equat ion, it is not ext remely CPU
int ensive and can represent LLE quit e well.
The NRTL equat ion in UniSim Design has t he following form:
Due t o t he mat hemat i cal st r uct ur e of t he NRTL equat i on, i t
can pr oduce er r oneous mul t i pl e mi sci bi l i t y gaps.
(A.26)
Unlike t he van Laar
equat ion, NRTL can be
used for dilut e syst ems
and hydrocarbon- alcohol
mixt ures, alt hough it may
not be as good for
alcohol- hydrocarbon
syst ems as t he Wilson
equat ion.
i
ln
t
ji
x
j
G
ji
j 1 =
n
x
k
G
ki
k 1 =
n
--------------------
x
j
G
ij
x
k
G
kj
k 1 =
n
----------------- t
ij
t
mj
x
m
G
mj
m 1 =
n
x
k
G
kj
k 1 =
n
--------------------------
\ .
|
|
|
|
|
|
| |
j 1 =
n
+ =
A- 31
where:
G
ij
=
=
x
i
a
ij
component s i and j ( cal/ gmol)
b
ij
i and j ( cal/ gmol- K)
= NRTL non- randomness const ant for binary int eract ion not e t hat
for all binaries
The five adj ust able paramet ers for t he NRTL equat ion in UniSim Design
are t he a
ij
, a
j i
, b
ij
, b
j i
, and t erms. The equat ion uses paramet er
values st ored in UniSim Design or any user supplied value for furt her
fit t ing t he equat ion t o a given set of dat a.
UNI QUAC
The UNI QUAC ( UNI versal QUAsi Chemical) equat ion proposed by
Abrams and Prausnit z in 1975 uses st at ist ical mechanics and t he quasi-
chemical t heory of Guggenheim t o represent t he liquid st ruct ure. The
equat ion is capable of represent ing LLE, VLE and VLLE wit h accuracy
comparable t o t he NRTL equat ion, but wit hout t he need for a non-
randomness fact or. The UNI QUAC equat ion is significant ly more
det ailed and sophist icat ed t han any of t he ot her act ivit y models. I t s
main advant age is t hat a good represent at ion of bot h VLE and LLE can
be obt ained for a large range of non- elect rolyt e mixt ur es using only t wo
adj ust able paramet ers per binary. The fit t ed paramet ers usually exhibit
a smaller t emperat ure dependence which makes t hem more valid for
ext rapolat ion purposes.
The UNI QUAC equat ion ut ilizes t he concept of local composit ion as
proposed by Wilson. Since t he primary concent rat ion variable is a
surface fract ion as opposed t o a mole fract ion, it is applicable t o
syst ems cont aining molecules of very different sizes and shape, such as
polymer solut ions. The UNI QUAC equat ion can be applied t o a wide
range of mixt ures cont aining H
2
O, alcohols, nit riles, amines, est ers,
ket ones, aldehydes, halogenat ed hydrocarbons and hydrocarbons.
UniSim Design cont ains t he following four- paramet er ext ended form of
i
t
ij
o
ij
| | exp
t
ij
a
ij
b
ij
T +
RT
----------------
o
ij
o
ij
o
ji
=
o
ij
A- 32
t he UNI QUAC equat ion. The four adj ust able paramet ers for t he
UNI QUAC equat ion in UniSim Design are t he a
ij
and a
j i
t erms
( t emperat ure independent ) , and t he b
ij
and b
j i
t erms ( t emperat ure
dependent ) .
The equat ion uses paramet er values st ored in UniSim Design or any
user supplied value for furt her fit t ing t he equat ion t o a given set of
dat a.
where:
x
i
L
j
= 0.5Z( r
j
- q
j
) - r
j
+ 1
=
=
=
Z = 10. 0 co- ordinat ion number
a
ij
b
ij
q
i
= van der Waals area paramet er - Aw
i
/ ( 2. 5e9)
A
w
= van der Waals area
r
i
= van der Waals volume paramet er - Vw
i
/ ( 15. 17)
V
w
= van der Waals volume
(A.27)
i
ln
u
i
x
i
----
\ .
| |
ln 0.5Zq
i
u
i
u
i
----
\ .
| |
L
i
u
i
x
i
----
\ .
| |
L
j
x
j
q
i
1.0 u
j
t
ji
j 1 =
n
ln
\ .
|
|
| |
q
i
u
j
t
ij
u
k
t
kj
k 1 =
n
----------------
\ .
|
|
|
|
|
|
| |
j 1 =
n
+
j 1 =
n
+ ln + =
i
u
i
q
i
x
i
q
j
x
j
j
-----------
t
ij
a
ij
b
ij
T +
RT
---------------- exp
u
i
r
i
x
i
r
j
x
j
j
-----------
A- 33
Van Laar
The van Laar equat ion was t he first Gibbs excess energy represent at ion
wit h physical significance. The van Laar equat ion in UniSim Design is a
modified form of t hat described in Phase Equilibrium in Process
Design by H. R. Null. This equat ion fit s many syst ems quit e well,
part icularly for LLE component dist ribut ions. I t can be used for syst ems
t hat exhibit posit ive or negat ive deviat ions from Raoult ' s Law, however,
it cannot predict maxima or minima in t he act ivit y coefficient .
Therefore, it generally performs poorly for syst ems wit h halogenat ed
hydrocarbons and alcohols. Due t o t he empirical nat ure of t he equat ion,
caut ion should be exercised in analyzing mult i- component syst ems. I t
also has a t endency t o predict t wo liquid phases when t hey do not
exist .
The van Laar equat ion has some advant ages over t he ot her act ivit y
models in t hat it requires less CPU t ime and can represent limit ed
miscibilit y as well as t hree phase equilibrium. UniSim Design uses t he
following ext ended, mult i- component form of t he van Laar equat ion.
where:
x
i
A
i
=
B
i
=
E
i
= - 4.0 if A
i
and B
i
< 0. 0, ot herwise 0. 0
z
i
=
a
ij
component s i and j
b
ij
i and j [ 1/ K]
(A.28)
The van Laar equat ion
also performs poorly for
dilut e syst ems and
cannot represent many
common syst ems, such
as alcohol- hydrocarbon
mixt ures, wit h accept able
accuracy.
i
ln A
i
1.0 z
i
| |
2
1.0 E
i
z
i
+ ( ) =
i
x
j
a
ij
b
ij
T + ( )
1.0 x
i
( )
--------------------
j 1 =
n
x
j
a
ji
b
ji
T + ( )
1.0 x
i
( )
--------------------
j 1 =
n
A
i
x
i
A
i
x
i
B
i
1.0 x
i
( ) + | |
------------------------------------
A- 34
a
j i
component s j and i
b
j i
j and i [ 1/ K]
The four adj ust able paramet ers for t he van Laar equat ion in UniSim
Design are t he a
ij
, a
j i
, b
ij
, and b
j i
t erms. The equat ion will use
paramet er values st ored in UniSim Design or any user supplied value
for furt her fit t ing t he equat ion t o a given set of dat a.
Wilson
The Wilson equat ion, pr oposed by Grant M. Wilson in 1964, was t he
first act ivit y coefficient equat ion t hat used t he local composit ion model
t o derive t he Gibbs Excess energy expression. I t offers a
t hermodynamically consist ent approach t o predict ing mult i- component
behaviour fr om regressed binary equilibrium dat a. Our experience also
shows t hat t he Wilson equat ion can be ext rapolat ed wit h reasonable
confidence t o ot her operat ing regions wit h t he same set of regressed
energy paramet er s.
Alt hough t he Wilson equat ion is more complex and requires more CPU
t ime t han eit her t he van Laar or Margules equat ions, it can represent
almost all non- ideal liquid solut ions sat isfact orily except elect r olyt es
and solut ions exhibit ing limit ed miscibilit y ( LLE or VLLE) . I t performs an
excellent j ob of pr edict ing t ernary equilibrium using paramet ers
regressed fr om binary dat a only.
The Wilson equat ion gives similar result s as t he Margules and van Laar
equat ions for weak non- ideal syst ems, but consist ent ly out performs
t hem for increasingly non- ideal syst ems.
The Wilson equat ion in UniSim Design requires t wo t o four adj ust able
paramet ers per binary. The four adj ust able paramet ers for t he Wilson
equat ion in UniSim Design are t he a
ij
and a
j i
( t emperat ure independent )
t erms, and t he b
ij
and b
j i
t erms ( t emperat ure dependent ) . Depending
upon t he available informat ion, t he t emperat ure dependent paramet ers
may be set t o zero.
Alt hough t he Wilson equat ion cont ains t erms for t emperat ure
dependency, caut ion should be exercised when ext rapolat ing. The
The Wilson equat ion
cannot be used for
problems involving liquid-
liquid equilibrium.
Set t ing all four
paramet ers t o zero does
not reduce t he binary t o
an ideal solut ion, but
maint ains a small effect
due t o molecular size
differences represent ed
by t he rat io of molar
volumes.
A- 35
Wilson act ivit y model in UniSim Design has t he following form:
where:
A
ij
=
x
i
a
ij
b
ij
V
i
= molar volume of pure liquid component i in m
3
/ kgmol ( lit res/
gmol)
The equat ion uses paramet er values st ored in UniSim Design or any
user supplied value for furt her fit t ing t he equat ion t o a given set of
dat a.
Henrys Law
Henry' s Law cannot be select ed explicit ly as a propert y met hod in
UniSim Design. However, UniSim Design uses Henry' s Law when an
act ivit y model is select ed and "non- condensable" component s are
included wit hin t he component list .
UniSim Design considers t he following component s " non- condensable" :
(A.29)
Component Si mul at i on Name
CH
4
Met hane
C
2
H
6
Et hane
C
2
H
4
Et hylene
C
2
H
2
Acet ylene
H
2
Hydrogen
He Helium
i
ln 1.0 x
j
A
ij
x
k
A
ki
x
j
A
kj
j 1 =
n
----------------
k 1 =
n
j 1 =
n
ln =
i
V
j
V
i
---
a
ij
b
ij
T + ( )
RT
-------------------- exp
A- 36
The ext ended Henr y' s Law equat ion in UniSim Design is used t o model
dilut e solut e/ solvent int eract ions. "Non- condensable" component s are
defined as t hose component s t hat have cr it ical t emperat ur es below t he
t emperat ure of t he syst em you are modeling. The equat ion has t he
following form:
where:
i = solut e or "non- condensable" component
j = solvent or condensable component
H
ij
= Henry' s coefficient bet ween i and j in kPa
A = A coefficient ent ered as a
ij
in t he paramet er mat rix
B = B coefficient ent ered as a
j i
C = C coefficient ent ered as b
ij
D = D coefficient ent ered as b
j i
T = t emperat ure in degrees K
An example of t he use of Henry' s Law coefficient s is illust rat ed below.
The NRTL act ivit y model is select ed as t he propert y met hod. Ther e are
t hree component s in t he Fluid Package, one of which, et hane, is a "non-
condensable" component . On t he Binary Coeffs t ab of t he Fluid Package
propert y view, you can view t he Henry' s Law coefficient s for t he
int eract ion of et hane and t he ot her component s.
By select ing t he A
i j
radio but t on, you can view/ edit t he A and B
coefficient s. Select t he B
i j
radio but t on t o ent er or view t he C and D
Ar Argon
N
2
Nit rogen
O2 Oxygen
NO NO
H
2
S H
2
S
CO
2
CO
2

CO CO
(A.30)
Component Si mul at i on Name
H
ij
ln A
B
T
-- C T ( ) DT + ln + + =
A- 37
coefficient s in t he Henry' s Law equat ion.
I f UniSim Design does not cont ain pre- fit t ed Henry' s Law coefficient s
and Henry' s Law dat a is not available, UniSim Design est imat es t he
missing coefficient s. To est imat e a coefficient ( A or B in t his case) ,
select t he A
ij
radio but t on, highlight a binary pair and press t he
I ndividual Pair but t on. The coefficient s are regressed t o fugacit ies
calculat ed using t he Chao- Seader/ Prausnit z- Shair correlat ions for
st andard st at e fugacit y and Regular Solut ion. To supply your own
coefficient s you must ent er t hem direct ly int o t he A
ij
and B
ij
mat rices,
as shown previously.
No int eract ion bet ween "non- condensable" component pairs is t aken
int o account in t he VLE calculat ions.
A. 3. 3 Act ivit y Model Vapour Phase
Opt ions
There ar e several models available for calculat ing t he Vapour Phase in
conj unct ion wit h t he select ed liquid act ivit y model. The select ion
depends on specific considerat ions of your syst em. However, in cases
when you ar e operat ing at moderat e pressures ( less t han 5 at m) ,
select ing I deal Gas should be sat isfact ory. The choices are described in
t he following sect ions:
Fi gur e A. 4
UniSim Design
does not cont ain a
pre- fit t ed Henry' s
Law A coefficient
for t he et hane/
et hanol pair. You
can est imat e it or
provide your own
value.
Henry' s
Law A
coefficient
for t he
int eract ion
bet ween C
2

and H
2
O.
Normal binary
int eract ion
coefficient for
t he H
2
O/
Et hanol pair.
C
2
is a "non- condensable"
component . Henry' s Law
is used for t he int eract ion
bet ween C
2
and t he ot her
component s in t he Fluid
Package.
Henry' s Law B
coefficient for t he
int eract ion
bet ween C
2
and
H
2
O.
Henry' s Law D
coefficient for t he
int eract ion bet ween
C
2
and H
2
O.
Henry' s Law C
coefficient for
t he int eract ion
bet ween C
2
and
H
2
O.
A- 38
I deal
The ideal gas law is used t o model t he vapour phase. This model is
appropriat e for low pressures and for a vapour phase wit h lit t le
int ermolecular int eract ion.
Peng Robinson, SRK, or RK
To model non- idealit ies in t he vapour phase, t he PR, SRK, or RK opt ions
can be used in conj unct ion wit h an act ivit y model. The PR and SRK
vapour phase models handle t he same t ypes of sit uat ions as t he PR and
SRK equat ions of st at e.
When select ing one of t hese opt ions ( PR, SRK, or RK) as t he vapour
phase model, you must ensure t hat t he binary int eract ion paramet ers
used for t he act ivit y model remain applicable wit h t he select ed vapour
model. You must keep in mind t hat all t he binary paramet ers in t he
UniSim Design Library are regr essed using t he ideal gas vapour model.
For applicat ions where you have compressors or t urbines being
modeled wit hin your Flowsheet , PR or SRK is superior t o eit her t he RK
or ideal vapour model. You obt ain more accurat e horsepower values by
using PR or SRK, as long as t he light component s wit hin your Flowsheet
can be handled by t he select ed vapour phase model ( i. e., C
2
H
4
or C
3
H
6

are fine, but alcohols are not modeled correct ly) .
Virial
The Vir ial opt ion enables you t o bet t er model vapour phase fugacit ies of
syst ems displaying st rong vapour phase int eract ions. Typically t his
occurs in syst ems cont aining carboxylic acids, or compounds t hat have
t he t endency t o form st able H
2
bonds in t he vapour phase. I n t hese
cases, t he fugacit y coefficient shows large deviat ions from idealit y, even
at low or moderat e pressures.
UniSim Design cont ains t emperat ure dependent coefficient s for
carboxylic acids. You can overwrit e t hese by changing t he Associat ion
( ii) or Solvat ion ( ij ) coefficient s from t he default values.
22
I f t he virial coefficient s need t o be calculat ed, UniSim Design cont ains
correlat ions using t he following pure component pr opert ies:
crit ical t emperat ure
crit ical pressure
dipole moment
mean radius of gyrat ion
For more informat ion,
refer t o Sect i on A. 3. 1 -
Equat i ons of St at e.
A- 39
associat ion paramet er
associat ion paramet er for each binary pair
This opt ion is rest rict ed t o syst ems where t he densit y is moderat e,
t ypically less t han one- hal f t he crit ical densit y. The Virial equat ion
used is valid for t he following range:
HF- PR
HF- PR opt ion is helping user t o bet t er model a syst em involving HF
( hydrogen fluoride) and it s mixt ures. While Peng- Robinson EOS is used
for ot her compounds except HF, a Honeywell modified LA (
23
Lencka and
Anderko, 1993) model was used t o model HF associat ion behavior in
t he vapor phase.
I n t he LA model, pr opert ies are derived from compressibilit y fact or Z,
which is decomposed int o t he regular physical cont ribut ion Z
PH
and
chemical cont ribut ion Z
CH
I n t he equat ion, Z
PH
is calculat ed by t he t radit ional PR equat ion wit h t he
model specified paramet ers
The chemical part is only apply t o HF compound and is given by
(A.31)
(A.32)
(A.33)
(A.34)
P
T
2
--
y
i
P
c
i
i 1 =
m
y
i
T
c
i
i 1 =
m
--------------- s
1 + =
CH PH
Z Z Z
( )
2 2
2
) (
b vb v RT
v T a
b v
v
Z
PH
+
=
( )
8
8
1
1
1
q
q a
Z
k
k
k
CH
+
+
=

=
A- 40
A. 3. 4 Semi- Empirical Met hods
The Chao- Seader
10
and Grayson- St reed
11
met hods are older, semi-
empirical met hods. The GS correlat ion is an ext ension of t he CS met hod
wit h special emphasis on H
2
. Only t he equilibrium result s produced by
t hese correlat ions is used by UniSim Design. The Lee- Kesler met hod is
used for liquid and vapour ent halpies and ent r opies as it s result s are
shown t o be superior t o t hose generat ed from t he CS/ GS correlat ions.
This met hod is also adopt ed by and recommended for use in t he API
Technical Dat a Book.
The following t able gives an approximat e range of applicabilit y for t hese
t wo met hods, and under what condit ions t hey are applicable.
The GS correlat ion is recommended for simulat ing heavy hydrocarbon
syst ems wit h a high H
2
cont ent , such as hydrot reat ing unit s. The GS
correlat ion can also be used for simulat ing t opping unit s and heavy
ends vacuum applicat ions.
The vapour phase fugacit y coefficient s are calculat ed wit h t he Redlich
Kwong equat ion of st at e. The pure liquid fugacit y coefficient s are
calculat ed using t he pr inciple of corresponding st at es. Modified acent ric
fact ors are included in UniSim Design' GS library for most component s.
Special funct ions are incorporat ed for t he calculat ion of liquid phase
fugacit ies for N
2
, CO
2
and H
2
S. These funct ions are rest rict ed t o
hydrocarbon mixt ures wit h less t han five percent of each of t he above
component s.
As wit h t he Vapour Pressure models, H
2
O is t reat ed using a
combinat ion of t he st eam t ables and t he kerosene solubilit y chart s from
t he API Dat a Book. This met hod of handling H
2
O is not very accurat e
for gas syst ems. Alt hough t hree phase calculat ions ar e perfor med for
Met hod Temp ( F) Temp ( C) Pr ess ( psi a) Pr ess ( k Pa)
CS 0 t o 500 - 18 t o 260 < 1,500 < 10,000
GS 0 t o 800 - 18 t o 425 < 3,000 < 20,000
Condi t i ons of Appl i cabi l i t y
For all hydrocarbons ( except
CH4) :
0. 5< Tr
i
< 1. 3 and Pr
mixt ure
< 0. 8
I f CH4 or H2 is present : molal average Tr < 0. 93
CH4 mole fract ion < 0. 3
mole fract ion dissolved gases < 0. 2
When predict ing K values for:
Paraffinic or Olefinic
Mixt ures
Aromat ic Mixt ures
liquid phase aromat ic mole fract ion
< 0. 5
liquid phase aromat ic mole fract ion
> 0. 5
A- 41
all syst ems, it is import ant t o not e t hat t he aqueous phase is always
t reat ed as pure H
2
O wit h t hese cor relat ions.
A. 3. 5 Vapour Pressure Propert y
Packages
Vapour pressure K value models may be used for ideal mixt ures at low
pressures. This includes hydr ocarbon syst ems such as mixt ures of
ket ones or alcohols where t he liquid phase behaves approximat ely
ideal. The models may also be used for first approximat ions for non-
ideal syst ems.
Vapour pressures used in t he calculat ion of t he st andard st at e fugacit y
are based on UniSim Design' library coefficient s and a modified form of
t he Ant oine equat ion. Vapour pressure coefficient s for hypocomponent
may be ent ered or calculat ed from eit her t he Lee- Kesler correlat ion for
hydrocarbons, t he Gomez-Thodos correlat ion for chemical compounds
or t he Reidel equat ion.
The Vapour Pressure opt ions include t he Modified Ant oine, BraunK10,
and EssoK packages.
Appr oximat e ranges of applicat ion for each vapour pressure model are
given below:
Modified Ant oine Vapour Pressure Model
The modified Ant oine equat ion assumes t he for m as set out in t he
The Lee- Kesl er model i s used f or ent hal py and ent r opy
cal cul at i ons f or al l v apour pr essur e model s and al l
component s w i t h t he ex cept i on of H
2
O, w hi ch i s t r eat ed
separ at el y w i t h t he st eam pr oper t y cor r el at i on.
Al l t hr ee phase cal cul at i ons ar e per f or med assumi ng t he
aqueous phase i s pur e H
2
O and t hat H
2
O sol ubi l i t y i n t he
hy dr ocar bon phase can be descr i bed usi ng t he k er osene
sol ubi l i t y equat i on f r om t he API Dat a Book ( Fi gur e 9A1.4) .
Model Temper at ur e Pr ess ( psi a) Pr ess ( k Pa)
Mod. Ant oine < 1.6 Tc
i
< 100 < 700
BraunK10 0F ( - 17. 78C) < 1. 6 Tc
i
< 100 < 700
EssoK < 1.6 Tc
i
< 100 < 700
Because all of t he
Vapour Pressure opt ions
assume an ideal vapour
phase, t hey are
classified as Vapour
Pressure Models.
A- 42
DI PPR dat a bank.
where:
A, B, C, D, E and F = fit t ed coefficient s
P
vap
= t he pressure in kPa
T = t he t emperat ure in K
These coefficient s are available for all UniSim Design library
component s. Vapour pr essure coefficient s for hypocomponent may be
ent ered or calculat ed from eit her t he Lee- Kesler correlat ion for
hydrocarbons, t he Gomez-Thodos correlat ion for chemical compounds,
or t he Reidel equat ion.
This model is applicable for low pressure syst ems t hat behave ideally.
For hydrocarbon component s t hat you have not provided vapour
pressure coefficient s for, t he model convert s t he Lee- Kesler vapour
pressure model direct ly. As such, crude and vacuum t owers can be
modeled wit h t his equat ion.
When using t his met hod for supercrit ical component s, it is
recommended t hat t he vapour pressure coefficient s be replaced wit h
Henry' s Law coefficient s. Changing Vapour Pressure coefficient s can
only be accomplished if your component is being inst alled as a
Hypot het ical.
(A.35) P
vap
ln A
B
T C +
---------- D T ET
F
+ ln + + =
All ent halpy and ent ropy
calculat ions are
performed using t he Lee-
Kesler model.
A- 43
Braun K10 Model
The Braun K10 model is st rict ly applicable t o heavy hydrocarbon
syst ems at low pressures. The model employs t he Braun convergence
pressure met hod, where, given t he normal boiling point of a
component , t he K value is calculat ed at syst em t emperat ure and 10
psia. The K10 value is t hen correct ed for pressure using pressure
correct ion chart s. The K values for any component s t hat ar e not
covered by t he chart s are calculat ed at 10 psia using t he modified
Ant oine equat ion and correct ed t o syst em condit ions using t he pr essure
correct ion chart s.
Accuracy suffers wit h t his model if t here are large amount s of acid
gases or light hydrocarbons. All t hree phase calculat ions assume t hat
t he aqueous phase is pure H
2
O and t hat H
2
O solubilit y in t he
hydrocarbon phase can be described using t he kerosene solubilit y
equat ion from t he API Dat a Book ( Figure 9A1. 4) .
Esso K Model
The Esso Tabular model is st rict ly applicable t o hydrocarbon syst ems at
low pressures. The model employs a modificat ion of t he Maxwell-
Bonnel vapour pressure model in t he following format :
where:
A
i
= fit t ed const ant s
T
b
i
= normal boiling point correct ed t o K = 12
T = absolut e t emperat ure
K = Wat son charact erisat ion fact or
(A.36)
The Lee- Kesler model is
used for ent halpy and
ent ropy calculat ions for
all component s wit h t he
except ion of H2O which is
t reat ed wit h t he st eam
t ables.
P
vap
log A
i
x
i
=
x
i
T
b
i
T
---- 0.0002867T
b
i
748.1 0.2145T
b
i
-------------------------------- =
A- 44
For heavy hydrocarbon syst ems, t he result s are comparable t o t he
modified Ant oine equat ion since no pressure correct ion is applied. For
nonhydrocarbon component s, t he K value is calculat ed using t he
Ant oine equat ion. Accuracy suffers if t here is a large amount of acid
gases or light hydr ocarbons. All t hree phase calculat ions are performed
assuming t he aqueous phase is pure H
2
O and t hat H
2
O solubilit y in t he
hydrocarbon phase can be described using t he kerosene solubilit y
equat ion from t he API Dat a Book ( Figure 9A1. 4) .
A. 3. 6 Miscellaneous - Special
Applicat ion Met hods
Amines Propert y Package
The amines package cont ains t he t hermodynamic models developed by
D. B. Robinson & Associat es for t heir propriet ary amine plant simulat or,
called AMSI M. Their amine propert y package is available as an opt ion
wit h UniSim Design giving you access t o a proven t hird part y propert y
package for reliable amine plant simulat ion, while maint aining t he
abilit y t o use UniSim Design' powerful flowsheet ing capabilit ies.
The chemical and physical propert y dat a base is rest rict ed t o amines
and t he following component s:
The equilibrium acid gas solubilit y and kinet ic paramet ers for t he
aqueous alkanolamine solut ions in cont act wit h H
2
S and CO
2
ar e
incorporat ed int o t heir pr opert y package. The amines proper t y package
is fit t ed t o ext ensive experiment al dat a gat hered from a combinat ion of
D. B. Robinson' s in- house dat a, several unpublished sources, and
numerous t echnical references.
The following t able gives t he equilibrium solubilit y limit at ions t hat
For t he Ami ne pr oper t y met hod, t he vapour phase i s
model ed usi ng t he PR model .
Component Cl ass Speci f i c Component s
Acid Gases CO
2
, H
2
S, COS, CS
2

Hydrocarbons CH
4
C
7
H
16

Olefins C
2
= , C
3
=
Mercapt ans M- Mercapt an, E- Mercapt an
Non Hydrocarbons H
2
, N
2
, O
2
, CO, H
2
O
The Lee- Kesler model is
used for ent halpy and
ent ropy calculat ions for
all component s wit h t he
except ion of H
2
O which is
t reat ed wit h t he st eam
t ables.
This met hod does not
allow any hypot het icals.
A- 45
should be observed when using t his propert y package:
* The amine mixtures, DEA/MDEA and MEA/MDEA are assumed to be primarily MDEA, so use the
MDEA value for these mixtures.
The absorpt ion of H
2
S and CO
2
by aqueous alkanolamine solut ions
involves exot hermic react ions. The heat effect s are an import ant fact or
in amine t r eat ing processes and are pr operly t aken int o account in t he
amines propert y package. Correlat ions for t he heat s of solut ion are set
up as a funct ion of composit ion and amine t ype. The correlat ions were
generat ed fr om exist ing published values or derived from solubilit y dat a
using t he Gibbs- Helmholt z equat ion.
The amines package incorporat es a specialized st age efficiency model
t o permit simulat ion of columns on a real t ray basis. The st age
efficiency model calculat es H
2
S and CO
2
component st age efficiencies
based on t he t ray dimensions given and t he calculat ed int ernal t ower
condit ions for bot h absorbers and st rippers. The individual component
st age efficiencies are a funct ion of pr essure, t emperat ure, phase
composit ions, flow rat es, physical proper t ies, mechanical t ray design
and dimensions as well as kinet ic and mass t ransfer paramet ers.
Since kinet ic and mass t ransfer effect s are primarily responsible for t he
H
2
S select ivit y demonst rat ed by amine solut ions, t his must be
account ed for by non unit y st age efficiencies.
St eam Package
UniSim Design includes t wo st eam packages:
ASME St eam
NBS St eam
Bot h of t hese propert y packages are rest rict ed t o a single component ,
namely H
2
O.
Al k anol ami ne
Al k anol ami ne
Concent r at i on ( w t % )
Aci d Gas Par t i al
Pr essur e ( psi a)
Temper at ur e
( F)
Monoet hanolamine, MEA 0 - 30 0.00001 - 300 77 - 260
Diet hanolamine, DEA 0 - 50 0.00001 - 300 77 - 260
Triet hanolamine, TEA 0 - 50 0.00001 - 300 77 - 260
Met hyldiet hanolamine,
MDEA*
0 - 50 0.00001 - 300 77 - 260
Diglycolamine, DGA 50 - 70 0.00001 - 300 77 - 260
DI soPropanolAmine, DI soA 0 - 40 0.00001 - 300 77 - 260
The dat a i s not cor r el at ed f or H
2
S and CO
2
l oadi ngs gr eat er
t han 1.0 mol e aci d gas/ mol e al k anol ami ne.
See Chapt er 8 - Col umn
of t he Uni Si m Desi gn
det ails on how t o specify
or have UniSim Design
calculat e t he st age
efficiencies.
A- 46 Ent hal py & Ent r opy Depar t ur e
A- 46
ASME St eam accesses t he ASME 1967 st eam t ables. The limit at ions of
t his st eam package are t he same as t hose of t he original ASME st eam
t ables, i. e., pressures less t han 15, 000 psia and t emperat ures great er
t han 32F ( 0C) and less t han 1, 500F.
The basic reference is t he book Thermodynamic and Transport
Propert ies of St eam - The American Societ y of Mechanical Engineer s -
Prepared by C. A. Meyer, R. B. McClint ock, G. J. Silvest ri and R. C. Spencer
Jr.
20
Select ing NBS_St eam uses t he NBS 1984 St eam Tables, which
report edly has bet t er calculat ions near t he Crit ical Point .
A. 4 Ent halpy & Ent ropy
Depart ure Calculat ions
The Ent halpy and Ent r opy calculat ions are performed rigorously by
UniSim Design using t he following exact t hermodynamic relat ions:
Wit h semi- empirical and vapour pr essure models, a pure liquid wat er
phase is generat ed and t he solubilit y of H
2
O in t he hydrocarbon phase
is det ermined from t he kerosene solubilit y model.
A. 4. 1 Equat ions of St at e
For t he Peng- Robinson Equat ion of St at e, t he ent halpy and ent ropy
depart ure calculat ions use t he following relat ions:
(A.37)
(A.38)
(A.39)
The I deal Gas Ent halpy
basis ( ) used by
UniSim Design is equal t o
t he ideal gas Ent halpy of
Format ion at 25C.
The I deal Gas Ent ropy
basis ( ) used by
UniSim Design is equal t o
t he ideal gas Ent ropy of
Format ion at 25C and 1
at m.
H
ID
S
ID
H H
ID
RT
-------------- Z 1
1
RT
----- T
T c
cP
\ .
| |
V
P V d
V
}
+ =
S S
ID
RT
-------------- Z ln
P
P
---- ln
1
R
--
T c
cP
\ .
| |
V
1
V
-- V d
V
}
+ =
H H
ID
RT
-------------- Z 1
1
2
1.5
bRT
-------------- a T
t d
da
V 2
0.5
1 + ( )b +
V 2
0.5
1 ( )b +
--------------------------
\ .
|
| |
ln =
The I deal Gas Ent halpy
basis ( H
I D
) used by
UniSim Design changes
wit h t emperat ure
according t o t he
coefficient s on t he TDep
t ab for each individual
component .
A- 47
where:

For t he SRK Equat ion of St at e:
A and B t erm definit ions are provided below:
where:
R = I deal Gas const ant
H = Ent halpy
S = Ent ropy
(A.40)
(A.41)
(A.42)
(A.43)
Peng- Robi nson Soav e- Redl i ch- Kw ong
b
i
a
i
a
ci
m
i
S S
ID
R
-------------- Z B ( ) ln
P
P
---- ln
A
2
1.5
bRT
--------------
T
a
--
t d
da V 2
0.5
1 + ( )b +
V 2
0.5
1 ( )b +
--------------------------
\ .
|
| |
ln =
a x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
( )
j 1 =
N
i 1 =
N
=
H H
ID
RT
-------------- Z 1
1
bRT
------- a T
da
dt
---- 1
b
V
-- +
\ .
| |
ln =
S S
ID
RT
-------------- Z b ( ) ln
P
P
---- ln
A
B
--
T
a
--
da
dt
---- 1
B
Z
-- +
\ .
| |
ln + =
0.077796
RT
ci
P
ci
-------- 0.08664
RT
ci
P
ci
--------
a
ci
o
i
a
ci
o
i
0.457235
RT
ci
( )
2
P
ci
------------- 0.42748
RT
ci
( )
2
P
ci
-------------
o
i
1 m
i
1 T
ri
0.5
( ) + 1 m
i
1 T
ri
0.5
( ) +
0.37646 1.54226e
i
0.26992e
i
2
+
0.48 1.574e
i
0.176e
i
2
+
a x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
( )
j 1 =
N
i 1 =
N
=
A- 48
subscript s:
I D = I deal Gas
o = reference st at e
PRSV
The PRSV equat ion of st at e is an ext ension of t he Peng- Robinson
equat ion using an ext ension of t he expression as shown below:
This result s in t he replacement of t he t er m in t he definit ions of t he A
and B t erms shown pr eviously by t he t erm shown above.
A. 4. 2 Act ivit y Models
The Liquid ent halpy and ent ropy for Act ivit y Models is based on t he
Cavet t Correlat ion as shown below:
for T
ri
< 1:
for T
ri
1:
(A.44)
(A.45)
(A.46)
k
o
i
1 k
i
1 T
r
0.5
( ) + | |
2
=
k
i
k
0i
1 T
ri
0.5
+ ( ) 0.7 T
ri
( ) =
k
0i
0.378893 1.4897153e
i
0.17131848e
i
2
0.0196554e
i
3
+ + =
o
i
o
i
H
L
H
ID
T
c
i
---------------- max
H
i
A
L
sb ( )
T
c
i
-------------------
H
i
A
L
sb ( )
T
c
i
------------------- ,
\ .
|
| |
=
>
H
L
H
ID
T
c
i
---------------- max
H
i
A
L
sb ( )
T
c
i
-------------------
H
i
A
L
sp ( )
T
c
i
------------------- ,
\ .
|
| |
=
A- 49
where:
a
1
, a
2
, a
3
= funct ions of t he Cavet t paramet er, fit t ed t o mat ch one
known heat of vapourizat ion
The Gas ent halpies and ent ropies are dependent on t he model chosen
t o repr esent t he vapour phase behaviour:
I deal Gas:
Redlich- Kwong:
Vir ial Equat ion:
where:
B = second virial coefficient of t he mixt ure
(A.47)
(A.48)
(A.49)
(A.50)
(A.51)
(A.52)
(A.53)
(A.54)
H
i
A
L
sb ( )
T
c
i
------------------- a
1
a
2
1 T
r
i
( )
1 a3 T
r
i
0.1 ( )
+ =
H
i
A
L
sp ( )
T
c
i
------------------- max 0 b
1
b
2
T
r
i
2
b
3
T
r
i
3
b
4
T
r
i
4
b
5
T
r
i
2
+ + + + , ( ) =
H H
ID
=
S S
ID
C
v
T d
T
---------
T1
T2
}
R
V
2
V
1
---- ln + = =
H H
ID
RT
-------------- Z 1
1.5
bRT
------- 1
b
V
-- +
\ .
| |
ln =
S S
ID
RT
-------------- Z b ( ) ln
P
P
---- ln
A
2B
----- 1
B
Z
-- +
\ .
| |
ln + =
H H
ID
RT
--------------
T
V B
---------
dB
dt
----- Z 1 ( ) + =
S S
ID
R
--------------
RT
V B
---------
dB
dT
----- R
V
V B
--------- ln R
V
V
---- ln + =
A- 50
A. 4. 3 Lee- Kesler Opt ion
The Lee and Kesler met hod is an effort t o ext end t he met hod originally
proposed by Pit zer t o t emperat ures lower t han 0. 8 T
r
. Lee and Kesler
expanded Pit zer' s met hod expressing t he compressibilit y fact or as:
where:
Z
o
= t he compressibilit y fact or of a simple fluid
Z
r
= t he compressibilit y fact or of a reference fluid
They chose t he reduced form of t he BWR equat ion of st at e t o represent
bot h Z
o
and Z
r
:
where:
The const ant s in t hese equat ions wer e det ermined using experiment al
compressibilit y and ent halpy dat a. Two set s of const ant s, one for t he
simple fluid ( ) and one for t he reference fluid
( ) wer e det ermined.
(A.55)
(A.56)
The SRK and PR are
given in Sect i on A.3.1
- Equat i ons of St at e.
Z Z
e
e
r
---- Z
r
Z
( ) + =
Select t his opt ion for
ent halpy calculat ion
when t he syst em
cont ains wat er ( polar) .
This met hod gives
accurat e predicit on of
ent halpies over a
st andard EOS met hod.
Z 1
B
V
r
----
C
V
r
2
----
D
V
r
5
----
D
T
r
3
V
r
3
--------- |

V
r
2
----
\ .
|
| |
e
V
r
2
----
\ .
| |
+ + + + =
V
r
VP
c
RT
c
------- =
B b
1
b
2
T
r
----
b
3
T
r
2
----
b
4
T
r
4
---- =
C c
1
c
2
T
r
---
c
3
T
r
3
---- + =
D d
1
d
2
T
r
---- + =
e
0
0 =
e
r
0.3978 n-C
8
, =
A- 51
The Ent halpy and Ent r opy depart ures are comput ed as follows:
For mixt ures, t he Crit ical Pr opert ies are defined as follows:
Fugacit y Coefficient
The fugacit y coefficient calculat ions for SRK and Peng Robinson models
is shown below.
(A.57)
(A.58)
(A.59)
H H
ID
RT
c
-------------- T
r
Z 1
b
2
2
b
3
T
r
---- 3
b
4
T
r
2
---- + +
T
r
V
r
---------------------------
c
2
3
c
3
T
r
2
----
2T
r
V
r
2
---------------
d
2
5T
r
V
r
5
----------- 3E +
)

`

=
S S
ID
R
-------------- Z ln
P
P
----
\ .
| |
ln
b
1
b
3
T
r
2
---- 2
b
4
T
r
3
---- + +
V
r
------------------------
c
1
3
c
3
T
r
2
----
2V
r
2
---------------
d
1
5V
r
2
------- 2E + =
E
c
4
2T
r
3
-------- | 1 | 1

V
r
2
---- + +
\ .
|
| |
e
V
r
----
\ .
| |
+
)

`

=
e x
i
e
i
i 1 =
N
=
z
c
i
0.2905 0.0851e
i
=
V
c
i
Z
c
i
RT
c
i
P
c
i
------------- =
V
c
1
8
-- x
i
x
j
V
c
i
1
3
--
V
c
j
1
3
--
+
\ .
|
| |
3
j 1 =
N
i 1 =
N
=
T
c
1
8V
c
------ x
i
x
j
V
c
i
1
3
--
V
c
j
1
3
--
+
\ .
|
| |
3
T
c
i
T
c
j
( )
0.5
j 1 =
N
i 1 =
N
=
P
c
0.2905 0.085e ( )
RT
c
V
c
------- =
A- 52 Phy si cal & Tr anspor t Pr oper t i es
A- 52
Soave- Redlich- Kwong
Peng Robinson
A. 5 Physical & Transport
Propert ies
The physical and t ransport propert ies t hat UniSim Design calculat es for
a given phase are viscosit y, densit y, t hermal conduct ivit y, and surface
t ension. The models used for t he t ransport propert y calculat ions are all
pre- select ed t o yield t he best fit for t he syst em under considerat ion. For
example, t he corresponding st at es model proposed by Ely and Hanley is
used for viscosit y predict ions of light hydrocarbons ( NBP< 155) , t he Twu
met hodology for heavier hydrocarbons, and a modificat ion of t he
Let sou- St iel met hod for predict ing t he liquid viscosit ies of non- ideal
chemical syst ems.
A complet e descript ion of t he models used for t he predict ion of t he
t ransport propert ies can be found in t he references list ed in each sub-
sect ion. All t hese models are modified by Honeywell t o improve t he
accuracy of t he correlat ions.
I n t he case of mult iphase st reams, t he t ransport propert ies for t he
mixed phase are meaningless and are report ed as < empt y> , alt hough
t he single phase propert ies are known. There is an except ion wit h t he
pipe and heat exchanger operat ions. For t hree- phase fluids, UniSim
Design uses empirical mixing rules t o det ermine t he apparent
propert ies for t he combined liquid phases.
(A.60)
(A.61)
|
i
ln Z
Pb
RT
-----
\ .
| |
ln Z 1 ( )
b
i
b
---
a
bRT
-------
1
a
-- 2a
i
0.5
x
j
a
j
0.5
1 k
ij
( )
j 1 =
N
\ .
|
|
| |
b
i
b
--- 1
b
V
-- +
\ .
| |
ln + =
|
i
ln Z
Pb
RT
-----
\ .
| |
ln Z 1 ( )
b
i
b
---
a
2
1.5
bRT
--------------
1
a
-- 2a
i
0.5
x
j
a
j
0.5
1 k
ij
( )
j 1 =
N
\ .
|
|
| |
b
i
b
---
V 2
0.5
1 + ( )b +
V 2
0.5
1 ( )b
-------------------------- ln + =
A- 53
A. 5. 1 Liquid Densit y
Sat urat ed liquid volumes are obt ained using a corresponding st at es
equat ion developed by R. W. Hankinson and G. H. Thompson
13
which
explicit ly relat es t he liquid volume of a pure component t o it s reduced
t emperat ure and a second paramet er t ermed t he charact erist ic volume.
This met hod is adopt ed as an API st andard. The pure compound
paramet ers needed in t he corresponding st at es liquid densit y
( COSTALD) calculat ions are t aken from t he original t ables published by
Hankinson and Thompson, and t he API Dat a Book for component s
cont ained in UniSim Design' library.
The paramet ers for hypot het ical component s are based on t he API
gravit y and t he generalized Lu equat ion. Alt hough t he COSTALD
met hod was developed for sat urat ed liquid densit ies, it can be applied
t o sub- cooled liquid densit ies, i. e., at pressures great er t han t he vapour
pressure, using t he Chueh and Prausnit z correct ion fact or for
compressed fluids. I t is used t o predict t he densit y for all syst ems
whose pseudo- reduced t emperat ure is below 1. 0. Above t his
t emperat ure, t he equat ion of st at e compressibilit y fact or is used t o
calculat e t he liquid densit y.
Hypocomponent s generat ed in t he Oil Charact erizat ion Environment
have t heir densit ies eit her calculat ed fr om int er nal corr elat ions or
generat ed from input curves. Given a bulk densit y, t he densit ies of t he
hypocomponent are adj ust ed such t hat :
The charact erist ic volume for each hypocomponent is calculat ed using
t he adj ust ed densit ies and t he physical proper t ies. The calculat ed
charact erist ic volumes are t hen adj ust ed such t hat t he bulk densit y
calculat ed fr om t he COSTALD equat ion mat ches t he densit y calculat ed
using t he above equat ion. This ensures t hat a given volume of fluid
cont ains t he same mass whet her it is calculat ed wit h t he sum of t he
component densit ies or t he COSTALD equat ion.
A. 5. 2 Vapour Densit y
The densit y for all vapour syst ems at a given t emperat ure and pressure
is calculat ed using t he compressibilit y fact or given by t he equat ion of
st at e or by t he appropriat e vapour phase model for Act ivit y Models.
(A.62)
bulk
1.0
x
i
i
-----
---------- =
A- 54
A. 5. 3 Viscosit y
UniSim Design aut omat ically select s t he model best suit ed for
predict ing t he phase viscosit ies of t he syst em under st udy. The model
select ed is from one of t he t hree available in UniSim Design: a
modificat ion of t he NBS met hod ( Ely and Hanley) , Twu' s model, or a
modificat ion of t he Let sou- St iel correlat ion. UniSim Design select s t he
appropriat e model using t he following crit eria:
All of t he models are based on corresponding st at es principles and are
modified for more reliable applicat ion. I nt ernal validat ion showed t hat
t hese models yielded t he most reliable result s for t he chemical syst ems
shown. Viscosit y predict ions for light hydrocarbon liquid phases and
vapour phases were found t o be handled more reliably by an in- house
modificat ion of t he original Ely and Hanley model, heavier hydrocarbon
liquids were more effect ively handled by Twu' s model, and chemical
syst ems were more accurat ely handled by an in- house modificat ion of
t he original Let sou- St iel model.
A complet e descript ion of t he original corresponding st at es ( NBS)
model used for viscosit y predict ions is present ed by Ely and Hanley in
t heir NBS publicat ion. The original model is modified t o eliminat e t he
it erat ive procedure for calculat ing t he syst em shape fact ors. The
generalized Leech- Leland shape fact or models are replaced by
component specific models. UniSim Design const ruct s a PVT map for
each component using t he COSTALD for t he liquid region. The shape
fact ors are adj ust ed such t hat t he PVT map can be reproduced using
t he reference fluid.
The shape fact ors for all t he library component s are already regressed
and included in t he Pure Component Library. Hypocomponent shape
fact ors are regressed using est imat ed viscosit ies. These viscosit y
est imat ions are funct ions of t he hypocomponent Base Propert ies and
Crit ical Propert ies.
Hypocomponent s generat ed in t he Oil Charact erizat ion Environment
have t he addit ional abilit y of having t heir shape fact ors regressed t o
mat ch kinemat ic or dynamic viscosit y assays.
The general model employs CH
4
as a reference fluid and is applicable t o
t he ent ire range of non- polar fluid mixt ures in t he hydrocarbon
Chemi cal Sy st em Vapour Phase Li qui d Phase
Lt Hydrocarbons ( NBP< 155F) Mod Ely & Hanley Mod Ely & Hanley
Hvy Hydrocarbons ( NBP> 155F) Mod Ely & Hanley Twu
Non- I deal Chemicals Mod Ely & Hanley Mod Let sou- St iel
A- 55
indust ry. Accuracy for highly aromat ic or napht henic cr udes is increased
by supplying viscosit y curves when available, since t he pure component
propert y generat ors were developed for average crude oils. The model
also handles H
2
O and acid gases as well as quant um gases.
Alt hough t he modified NBS model handles t hese syst ems very well, t he
Twu met hod was found t o do a bet t er j ob of predict ing t he viscosit ies of
heavier hydrocarbon liquids. The Twu model
9
is also based on
corresponding st at es pr inciples, but has implement ed a viscosit y
correlat ion for n- alkanes as it s r eference fluid inst ead of CH
4
. A
complet e descript ion of t his model is given in t he paper ent it led
I nt ernally Consist ent Correlat ion for Predict ing Liquid Viscosit ies of
Pet roleum Fract ions
15
.
For chemical syst ems t he modified NBS model of Ely and Hanley is used
for pr edict ing vapour phase viscosit ies, whereas a modified form of t he
Let sou- St iel model is used for predict ing t he liquid viscosit ies. This
met hod is also based on corresponding st at es principles and was found
t o perform sat isfact orily for t he component s t est ed.
The shape fact ors cont ained in t he UniSim Design Pure Component
Library are fit t o mat ch experiment al viscosit y dat a over a br oad
operat ing range. Alt hough t his yields good viscosit y predict ions as an
average over t he ent ire range, improved accuracy over a nar row
operat ing range can be achieved by using t he Tabular feat ures.
A. 5. 4 Liquid Phase Mixing Rules
for Viscosit y
The est imat es of t he apparent liquid phase viscosit y of immiscible
Hydrocarbon Liquid - Aqueous mixt ures are calculat ed using t he
following "mixing rules" :
I f t he volume fract ion of t he hydrocarbon phase is great er t han
or equal t o 0. 5, t he following equat ion is used
17
:
where:
= apparent viscosit y
= viscosit y of Hydrocarbon phase
= volume fract ion Hydrocarbon phase
(A.63)
t he Tabular feat ures, refer
t o Chapt er 2 - Fl ui d
Pack age.
eff

oil
e
3.6 1 v
oil
( )
=
eff
oil
v
oil
A- 56
I f t he volume fract ion of t he hydrocarbon phase is less t han 0.33,
t he following equat ion is used
18
:
where:
= apparent viscosit y
= viscosit y of Hydrocarbon phase
= viscosit y of Aqueous phase
= volume fract ion Hydrocarbon phase
I f t he volume of t he hydrocarbon phase is bet ween 0. 33 and
0. 5, t he effect ive viscosit y for combined liquid phase is
calculat ed using a weight ed average bet ween Equat i on ( A.63)
and Equat i on ( A. 64) .
The remaining pr opert ies of t he pseudo phase are calculat ed as follows:
A. 5. 5 Thermal Conduct ivit y
As in viscosit y predict ions, a number of different models and
component specific correlat ions are implement ed for predict ion of liquid
and vapour phase t hermal conduct ivit ies. The t ext by Reid, Prausnit z
and Poling
16
was used as a general guideline in det ermining which
model was best suit ed for each class of component s.
For hydrocarbon syst ems t he corresponding st at es met hod proposed by
Ely and Hanley
14
is generally used. The met hod requires molecular
weight , acent r ic fact or and ideal heat capacit y for each component .
These paramet ers are t abulat ed for all library component s and may
eit her be input or calculat ed for hypot het ical component s. I t is
recommended t hat all of t hese paramet ers be supplied for non-
hydrocarbon hypot het icals t o ensure reliable t hermal conduct ivit y
coefficient s and ent halpy depart ures.
(A.64)
(A.65)
eff
1 2.5v
oil
oil
0.4
H
2
O
+
oil

H
2
O
+
--------------------------
\ .
|
| |
+
H
2
O
=
eff
oil
H
2
O
v
oil
MW
eff
x
i
MW
i
=
eff
1
x
i
i
---
\ .
| |
------------- =
C
p
eff
x
i
C
p
i
=
(molecular weight)
(mixture density)
(mixture specific heat)
A- 57
The modificat ions t o t he met hod are ident ical t o t hose for t he viscosit y
calculat ions. Shape fact ors calculat ed in t he viscosit y rout ines are used
direct ly in t he t hermal conduct ivit y equat ions. The accuracy of t he
met hod depends on t he consist ency of t he original PVT map.
The Sat o- Reidel met hod
16
is used for liquid phase t her mal conduct ivit y
predict ions of glycols and acids, t he Lat ini et al. met hod
16
is used for
est ers, alcohols and light hydrocarbons in t he range of C
3
- C
7
, and t he
Missenard and Reidel met hod
16
is used for t he remaining component s.
For vapour phase t hermal conduct ivit y predict ions, t he Misic and
Thodos, and Chung et al.
16
met hods are used ( except for H2O, C1, H2,
CO2, NH3 which use a polynomial for pur e component s) . The effect of
higher pressur e on t hermal conduct ivit ies is t aken int o account by t he
Chung et al. met hod.
For liquid phase t hermal conduct ivit y predict ions:
For pure wat er, use t he St eam Tables.
When wat er and DEG exist at t he same t ime, some special
t reat ment for t hose t wo compounds.
For wat er, DEG, C1, C2, C3, 3M- 3Epent ane, propene, TEG, EG,
He, H2, Et hylene, Ammonia, a polynomial is used.
For Hydrocarbon wit h MW > 140 and TR < 0. 8, a modified
Missenar d & Reidel met hod is used. Because t he Missenar d and
Reidel met hod needs Cp at st andard condit ion, UniSim Design
does not use t he unmodified version.
For Alcohol, Est er and Hydrocarbons not ment ioned in t he last
cat egory, Lat ini is used.
For ot hers, Sat o- Reidel is used.
A- 58
As wit h viscosit y, t he t hermal conduct ivit y for t wo liquid phases is
approximat ed by using empirical mixing rules for generat ing a single
pseudo liquid phase propert y. The t hermal conduct ivit y for an
immiscible binary of liquid phases is calculat ed by t he following
equat ion
21
:
where:
= liquid t hermal conduct ivit y of pure component i or j at
t emperat ure T
=
x
i
= mole fract ion of liquid i
V
i
= molar volume of liquid i
x
k
= mole fract ion of component k
V
k
= molar volume of component k
For a binary syst em t he equat ion simplifies t o:
(A.66)
(A.67)
L
i
|
i
|
j
k
ij
j
L
i
k
ij
2
1 k
i
( ) 1 k
j
( ) +
---------------------------- =
|
i
x
i
V
i
x
k
V
k
k 1 =
----------------
L
mi x
|
L
1
2
L
1
2|
L
1
|
L
2
12
|
L
2
2
L
2
+ + =
A- 59
A. 5. 6 Surface Tension
Surface t ensions for hydr ocarbon syst ems are calculat ed using a
modified form of t he Brock and Bird equat ion
8
. The equat ion expresses
t he surface t ension, , as a funct ion of t he reduced and crit ical
propert ies of t he component . The basic form of t he equat ion was used
t o regr ess paramet ers for each family of component s.
where:
= surface t ension ( dynes/ cm
2
)
T
BR
= reduced boiling point t emperat ure ( T
b
/ T
c
)
a = paramet er fit t ed for each chemical class
b = ( paramet er fit t ed for each chemical
class, expanded as a polynomial in acent ricit y)
For aqueous syst ems, UniSim Design employs a polynomial t o predict
t he surface t ension.
(A.68)
Uni Si m Desi gn pr edi ct s onl y l i qui d- vapour ( ai r ) sur f ace
t ensi ons.
o
o P
c
2 3
T
c
1 3
Q 1 T
R
( )
a
b =
o
Q 0.1207 1
T
BR
P
c
ln
1.0 T
BR
-------------------- +
\ .
| |
0.281 =
c
o
c
1
e c
2
e
2
c
3
e
3
+ + +
A- 60 Vol umet r i c Fl ow Rat e Cal cul at i ons
A- 60
A. 5. 7 Heat Capacit y
Heat Capacit y is calculat ed using a rigorous C
v
value whenever UniSim
Design can. The rigorous Cv is det ermined as:
However, when ever t his equat ion fails t o provide an answer, UniSim
Design falls back t o t he semi- ideal C
p
/ C
v
met hod by comput ing C
p
/ C
v

as C
p
/ ( C
p
- R) , which is only approximat e and valid for ideal gases.
Examples of when UniSim Design uses t he ideal met hod are:
Equat i on ( A. 69) fails t o ret urn an answer
The st ream has a solid phase
abs( dV/ dP) < 1e- 12
C
p
/ C
v
< 0. 1or C
p
/ C
v
> 20 - t his is out side t he range of
applicabilit y of t he equat ion used so UniSim Design falls back t o
t he ideal met hod
A. 6 Volumet ric Flow Rat e
Calculat ions
UniSim Design has t he abilit y t o int erpret and produce a wide
assort ment of flow rat e dat a. I t can accept several t ypes of flow rat e
informat ion for st r eam specificat ions as well as report back many
different flow rat es for st reams, t heir phases and t heir component s.
One drawback of t he large variet y available is t hat it oft en leads t o
some confusion as t o what exact ly is being specified or report ed,
especially when volumet r ic flow rat es are involved.
I n t he following sect ions, t he available flow rat es are list ed, each
corresponding densit y basis is explained, and t he act ual formulat ion of
t he flow rat e calculat ions is present ed. For volumet ric flow rat e dat a
t hat is not direct ly accept ed as a st ream specificat ion, a final sect ion is
provided t hat out lines t echniques t o convert your input t o mass flow
rat es.
(A.69) C
p
C
v
T
cv
cT
----
\ .
| |
P
2
cV
cP
-----
\ .
| |
T
------------- =
A- 61
A. 6. 1 Available Flow Rat es
Many t ypes of flow rat es appear in UniSim Design out put . However,
only a subset of t hese are available for st ream specificat ions.
Flow Rat es Report ed in t he Out put
The flow rat e t ypes available t hrough t he numerous report ing met hods
- propert y views, workbook, PFD, specsheet s, and so fort h are:
Molar Flow
Mass Flow
St d I deal Liq Vol Flow
Liq Vol Flow @St d Cond
Act ual Volume Flow
St d Gas Flow
Act ual Gas Flow
Flow Rat es Available for Specificat ion
The following flow rat e t ypes are available for st ream specificat ions:
Molar Flows
Mass Flows
LiqVol Flows
A. 6. 2 Liquid & Vapour Densit y
Basis
All calculat ions for volumet r ic st ream flows are based on densit y.
UniSim Design uses t he following densit y basis:
The v ol umet r i c f l ow r at e st andar d r ef er ence st at e i s def i ned as
60F and 1 at m w hen usi ng Fi el d uni t s or 15C and 1 at m w hen
Densi t y Basi s Descr i pt i on
St d I deal Li q
Mass Densi t y
This is calculat ed based on ideal mixing of pure
component ideal densit ies at 60F.
Li q Mass Densi t y
@St d Cond
This is calculat ed rigorously at t he st andard reference
st at e for volumet ric flow rat es.
Act ual Li qui d
Densi t y
This is calculat ed rigorously at t he flowing condit ions of
t he st ream ( i. e., at st ream T and P) .
St andar d Vapour
Densi t y
This is det ermined direct ly from t he I deal Gas law.
Act ual Vapour
Densi t y
This is calculat ed rigorously at t he flowing condit ions of
t he st ream ( i. e., at st ream T and P) .
Act ual Densit ies are
calculat ed at t he st ream
Temperat ure and
Pressure.
A- 62
usi ng SI uni t s.
Calculat ion of St andard & Act ual Liquid
Densit ies
The St andard and Act ual liquid densit ies are calculat ed rigorously at t he
appropriat e T and P using t he int ernal met hods of t he chosen pr opert y
package. Flow rat es based upon t hese densit ies aut omat ically t ake int o
account any mixing effect s exhibit ed by non- ideal syst ems. Thus, t hese
volumet ric flow rat es may be considered as "real world".
Calculat ion of St andard I deal Liquid
Mass Densit y
Cont rary t o t he rigorous densit ies, t he St andard I deal Liquid Mass
densit y of a st ream does not t ake int o account any mixing effect s due
t o it s simplist ic assumpt ions. Thus, flow rat es t hat are based upon it do
not account for mixing effect s and are more empirical in nat ure. The
calculat ion is as follows:
where:
x
i
= molar fract ion of component i
= pure component I deal Liquid densit y
UniSim Design cont ains I deal Liquid densit ies for all component s in t he
Pure Component Library ( Double click on t he component name in t he
basis and go t o t he Crit ical t ab on t he window t hat appears) . These
values are det ermined in one of t hree ways, based on t he
charact erist ics of t he component , as described below:
Case 1 - For any component t hat is a liquid at 60F and 1 at m,
t he dat a base cont ains t he densit y of t he component at 60F and
1 at m.
Case 2 - For any component t hat can be liquified at 60F and
pressures great er t han 1 at m, t he dat a base cont ains t he
densit y of t he component at 60F and Sat urat ion Pressure.
Case 3 - For any component t hat is non- condensable at 60F
under any pressure, i. e., 60F is great er t han t he cr it ical
t emperat ure of t he component , t he dat a base cont ains GPA
t abular values of t he equivalent liquid densit y. These densit ies
(A.70)
Ideal Density
Stream
1
x
i
i
Ideal
----------
---------------- =
i
Ideal
A- 63
were experiment ally det ermined by measuring t he displacement
of hydrocarbon liquids by dissolved non- condensable
component s.
For all hypot het ical component s, t he St andard Liquid densit y ( Liquid
Mass Densit y @St d Condit ions) in t he Base Propert ies is used in t he
I deal Liquid densit y ( St d I deal Liq Mass Densit y) calculat ion. I f a
densit y is not supplied, t he UniSim Design est imat ed liquid mass
densit y ( at st andard condit ions) is used. Special t reat ment is given by
t he Oil Charact erizat ion feat ure t o it s hypocomponent such t hat t he
ideal densit y calculat ed for it s st reams mat ch t he assay, bulk propert y,
and flow rat e dat a supplied in t he Oil Charact erizat ion Environment .
A. 6. 3 Formulat ion of Flow Rat e
Calculat ions
The various procedures used t o calculat e each of t he available flow
rat es are det ailed below, based on a known molar flow.
Molar Flow Rat e
Mass Flow
St d I deal Liq Vol Flow
This volumet ric flow rat e is calculat ed using t he ideal densit y of t he
st ream and t hus is somewhat empirical in nat ure.
(A.71)
(A.72)
(A.73)
For det ailed informat ion
for st ream correlat ion
refer t o t he Cor r el at i on
sect ion in t he Uni Si m
Oper at i ons Gui de.
Total Molar Flow Molar Flow
Stream
=
Mass Flow Total Molar Flow MW
Stream
=
Even if a st ream is all
vapour, it st ill has a Liq
Volume flow, based upon
t he st ream' s St andard
I deal Liquid Mass densit y,
whose calculat ion is
det ailed in t he previous
sect ion.
Std Ideal Liq Vol Flow
Total Molar Flow MW
Stream
Std Ideal Liq Mass Density

Stream
---------------------------------------------------------- =
A- 64
Liq Vol Flow ( St d Cond)
This volumet ric flowrat e is calculat ed using a rigorous densit y
calculat ed t hrough t he COSTALD met hod at st andard condit ions, and
reflect s non- ideal mixing effect s. The densit y and flow are report ed as
< empt y> if t he crit ical t emperat ure of any component in t he st ream is
below 15C ( / 60F) .
Act Volume Flow
This volumet ric flow rat e is calculat ed using a rigorous liquid densit y
calculat ion at t he act ual st ream T and P condit ions, and reflect s non-
ideal mixing effect s.
St andard Gas Flow
St andard gas flow is based on t he molar volume of an ideal gas at
st andard condit ions. I t is a direct conversion from t he st ream' s molar
flow rat e, based on t he following:
I deal Gas at 60F and 1 at m occupies 379. 46 ft
3
/ lbmole
I deal Gas at 15C and 1 at m occupies 23. 644 m
3
/ kgmole
Act ual Gas Flow
This volumet ric flow rat e is calculat ed using a rigorous vapour densit y
calculat ion at t he act ual st ream T and P condit ions, and reflect s non-
ideal mixing and compressibilit y effect s.
(A.74)
(A.75)
(A.76)
Liq Vol Flow (Std Cond)
Total Molar Flow MWStream
Liq Mass Density (Std Cond)
--------------------------------------------------------- =
Act Volume Flow
Molar Flow MW
Mass Density
--------------------------------- =
Actual Gas Flow
Molar Flow MW
Density
--------------------------------- =
A- 65
A. 6. 4 Volumet ric Flow Rat es as
Specificat ions
I f you require t hat t he flow rat e of your st ream be specified based on
act ual densit y or st andard densit y as opposed t o St andard I deal Mass
Liquid densit y, you must use one of t he following procedures:
Liq Vol Flow ( St d Cond)
1. Specify t he composit ion of your st ream.
2. Use t he st andar d ideal liquid mass densit y report ed for t he st ream
and calculat e t he corresponding mass flow rat e eit her manually, or
in t he SpreadSheet .
3. Use t his calculat ed mass flow as t he specificat ion for t he st ream.
Act Liquid Volume Flow
1. Specify t he composit ion and t he flowing condit ions ( T and P) of your
st ream.
2. Use t he densit y report ed for t he st ream and calculat e t he
corresponding mass flow rat e eit her manually, or in our
spreadsheet .
3. Use t his calculat ed mass flow as t he specificat ion for t he st ream.
A. 7 Flash Calculat ions
Rigorous t hree phase calculat ions are performed for all equat ions of
st at e and act ivit y models wit h t he except ion of Wilson' s equat ion, which
only performs t wo phase vapour- liquid calculat ions. As wit h t he Wilson
Equat ion, t he Amines and St eam propert y packages only support t wo
phase equilibrium calculat ions.
UniSim Design uses int ernal int elligence t o det ermine when it can
perform a flash calculat ion on a st ream, and t hen what t ype of flash
calculat ion needs t o be performed on t he st ream. This is based
complet ely on t he degrees of freedom concept . Once t he composit ion of
a st ream and t wo propert y variables are known, ( vapour fract ion,
t emperat ure, pressure, ent halpy or ent ropy) one of which must be
eit her t emperat ur e or pressure, t he t hermodynamic st at e of t he st ream
is defined. When UniSim Design recognizes t hat a st ream is
t hermodynamically defined, it performs t he correct flash aut omat ically
in t he background. You never have t o inst ruct UniSim Design t o
perform a flash calculat ion.
Specified variables can
only be re- specified by
you or t hrough Recycle
Adj ust , or SpreadSheet
operat ions. They do not
change t hrough any heat
or mat erial balance
calculat ions.
A- 66 Fl ash Cal cul at i ons
A- 66
Propert y variables can eit her be specified by you or back- calculat ed
from anot her unit operat ion. A specified variable is t reat ed as an
independent variable. All ot her st ream proper t ies are t r eat ed as
dependent variables and are calculat ed by UniSim Design.
I n t his manner, UniSim Design also recognizes when a st ream is
overspecified. For example, if you specify t hree st r eam pr opert ies plus
composit ion, UniSim Design pr int s out a warning message t hat an
inconsist ency exist s for t hat st ream. This also applies t o st reams where
an inconsist ency is creat ed t hrough UniSim Design calculat ions.
For example, if a st ream Temperat ure and Pressur e are specified in a
flowsheet , but UniSim Design back- calculat es a different t emperat ure
for t hat st ream as a result of an ent halpy balance across a unit
operat ion, UniSim Design generat es an I nconsist ency message.
A. 7. 1 T- P Flash Calculat ion
The independent variables for t his t ype of flash calculat ion are t he
t emperat ure and pressure of t he syst em, while t he dependent variables
are t he vapour fract ion, ent halpy, and ent ropy.
Wit h t he equat ions of st at e and act ivit y models, rigorous calculat ions
are performed t o det ermine t he coexist ence of immiscible liquid
phases and t he result ing component dist ribut ions by minimizat ion of
t he Gibbs free energy t erm. For vapour pressure models or t he semi-
empirical met hods, t he component dist ribut ion is based on t he
Kerosene solubilit y dat a ( Figure 9A1. 4 of t he API Dat a Book) .
I f t he mixt ure is single- phase at t he specified condit ions, t he propert y
package calculat es t he isot hermal compressibilit y ( dv/ dp) t o det ermine
if t he fluid behaves as a liquid or vapour. Fluids in t he dense- phase
region are assigned t he propert ies of t he phase t hat best represent s
Uni Si m Desi gn aut omat i cal l y per f or ms t he appr opr i at e f l ash
cal cul at i on w hen i t r ecogni zes t hat suf f i ci ent st r eam
i nf or mat i on i s k now n. Thi s i nf or mat i on i s ei t her speci f i ed by
t he user or cal cul at ed by an oper at i on.
Dependi ng on t he k now n st r eam i nf or mat i on, Uni Si m Desi gn
per f or ms one of t he f ol l ow i ng f l ashes: T- P, T- VF, T- H, T- S, P-
VF, P- H, or P- S.
I f a flash calculat ion is
performed on a st ream,
UniSim Design knows
all t he propert y values
of t hat st ream, i. e.,
t hermodynamic,
physical and t ransport
propert ies.
See Sect i on 2. 4. 4 -
St abi l i t y Test Tab for
opt ions on how t o
inst ruct UniSim Design t o
perform phase st abilit y
t est s.
A- 67
t heir current st at e.
A. 7. 2 Vapour Fract ion Flash
Vapour fract ion and eit her t emperat ur e or pressure are t he
independent variables for t his t ype of calculat ion. This class of
calculat ion embodies all fixed qualit y point s including bubble point s
( vapour pressure) and dew point s.
To perform bubble point calculat ion on a st ream of known composit ion,
simply specify t he Vapour Fract ion of t he st ream as 0. 0 and define t he
t emperat ure or pressure at which t he calculat ion is desired. For a dew
point calculat ion, simply specify t he Vapour Fract ion of t he st ream as
1. 0 and define t he t emperat ure or pressure at which t he dew point
calculat ion is desired. Like t he ot her t ypes of flash calculat ions, no
init ial est imat es are required.
The vapour fract ion is always shown in t erms of t he t ot al number of
moles. For example, t he vapour fract ion ( VF) represent s t he fract ion of
vapour in t he st ream, while t he fract ion, ( 1. 0 - VF) , represent s all ot her
phases in t he st ream ( i. e., a single liquid, 2 liquids, a liquid and a solid) .
Dew Point s
Given a vapour fract ion specificat ion of 1. 0 and eit her t emperat ur e or
pressure, t he propert y package calculat es t he ot her dependent variable
( P or T) . I f t emperat ure is t he second independent variable, UniSim
Design calculat es t he dew point pressure. Likewise, if pressure is t he
independent variable, t hen t he dew point t emperat ure is calculat ed.
Ret rograde dew point s may be calculat ed by specifying a vapour
fract ion of - 1. 0. I t is import ant t o not e t hat a dew point t hat is
ret rograde wit h respect t o t emperat ure can be normal wit h respect t o
pressure and vice versa.
The mat er i al sol i ds appear i n t he l i qui d phase of t w o- phase
mi x t ur es, and i n t he heavy ( aqueous/ sl ur r y ) phase of t hr ee-
phase sy st ems. Ther ef or e, w hen a separ at or i s sol ved usi ng
a T- P f l ash, t he vapour phase i s i dent i cal r egar dl ess of
w het her or not sol i ds ar e pr esent i n t he f eed t o t he f l ash
dr um.
Use caut ion in specifying
solids wit h syst ems t hat
are ot herwise all vapour.
Small amount s of non-
solids may appear in t he
"liquid" phase.
All of t he solids appear in
t he liquid phase.
A- 68
Bubble Point s/ Vapour Pressure
A vapour fract ion specificat ion of 0.0 defines a bubble point calculat ion.
Given t his specificat ion and eit her t emperat ure or pressure, t he
propert y package calculat es t he unknown T or P variable. As wit h t he
dew point calculat ion, if t he t emperat ure is known, UniSim Design
calculat es t he bubble point pressure and conversely, given t he
pressure, UniSim Design calculat es t he bubble point t emperat ure. For
example, by fixing t he t emperat ure at 100F, t he result ing bubble point
pressure is t he t rue vapour pressure at 100F.
Qualit y Point s
Bubble and dew point s are special cases of qualit y point calculat ions.
Temperat ures or pressures can be calculat ed for any vapour qualit y
bet ween 0. 0 and 1. 0 by specifying t he desired vapour fract ion and t he
corresponding independent variable. I f UniSim Design displays an error
when calculat ing vapour fract ion, t hen t his means t hat t he specified
vapour fract ion doesn' t exist under t he given condit ions, i. e., t he
specified pressure is above t he cricondenbar, or t he given t emperat ure
lies t o t he right of t he cricondent herm on a st andard P-T envelope.
A. 7. 3 Ent halpy Flash
Given t he ent halpy and eit her t he t emperat ure or pressure of a st ream,
t he propert y package calculat es t he unknown dependent variables.
Alt hough t he ent halpy of a st ream can be specified direct ly, it oft en
occurs as t he second propert y variable as a result of energy balances
around unit operat ions such as valves, heat exchanger s and mixers.
I f UniSim Design responds wit h an error message, and cannot find t he
specified propert y ( t emperat ure or pressure) , t his probably means t hat
an int ernally set t emperat ure or pressure bound was encount ered.
Since t hese bounds are set at quit e large values, t here is generally
some erroneous input t hat is direct ly or indirect ly causing t he problem,
such as an impossible heat exchange.
A. 7. 4 Ent ropy Flash
Given t he ent r opy and eit her t he t emperat ure or pressure of a st ream,
t he propert y package calculat es t he unknown dependent variables.
Vapour pr essur e and bubbl e poi nt pr essur e ar e sy nony mous.
UniSim Design calculat es
t he ret rograde condit ion
for t he specified vapour
qualit y if t he vapour
fract ion is input as a
negat ive number.
I f a specified amount of
energy is t o be added t o a
st ream, t his may be
accomplished by
specifying t he energy
st ream int o eit her a
Cooler/ Heat er or Balance
operat ion.
A- 69
A. 7. 5 Elect rolyt e Flash
The elect r olyt e st ream flash differ s from t he UniSim Design mat erial
st ream flash in t hat it specifically handles complex aqueous elect rolyt e
syst ems.
The UniSim Design OLI I nt erface package is an int erface t o t he OLI
Engine ( OLI Syst ems) t hat enables simulat ions wit hin UniSim Design
using t he full funct ionalit y and capabilit ies of t he OLI Engine for
flowsheet simulat ion.
When t he OLI _Elect rolyt e proper t y package is associat ed wit h mat er ial
st reams, t he st reams exclusively become elect rolyt e mat erial st reams
in t he flowsheet . That is, t he st ream conduct s a simult aneous phase
and react ion equilibrium flash. For t he model used and t he react ions
involved in t he flash calculat ion, refer t o t he Uni Si m Desi gn OLI
I nt er f ace Ref er ence Gui de.
An elect rolyt e mat erial st ream in UniSim Design can perform t he
following t ype of flashes:
TP Flash
PH Flash
TH Flash
PV Flash
TV Flash
Due t o t he involvement of react ions in t he st ream flash, t he equilibrium
st ream flash may result in a different molar flow and composit ion from
t he specified value. Therefore, mass and energy are conserved for an
elect rolyt e mat erial st ream against t he UniSim Design st ream for mass,
molar and energy balances.
Limit at ions exist in t he UniSim Design OLI I nt erface package in t he
calculat ion of t he st ream flash result s. The calculat ion for t he
elect rolyt e flash result s must fall wit hin t he following physical ranges t o
be valid.
composit ion of H
2
O in aqueous phase must be > 0. 65.
Temperat ure must be bet ween 0 and 300C.
Pressure must be bet ween 0 and 1500 at m.
I onic st rengt h must be bet ween 0 and 30 mole/ kg- H
2
O.
Refer t o Sect i on 1. 7 - Range of Appl i cabi l i t y of t he Uni Si m Desi gn
OLI I nt er f ace Ref er ence Gui de for more informat ion on t he
limit at ions of t he HEO models.
elect rolyt e flash and
aqueous
t hermodynamics.
A- 70
A. 7. 6 Handling of Wat er
Wat er is handled different ly depending on t he correlat ion being used.
The PR and PRSV equat ions ar e enhanced t o handle H
2
O rigorously
whereas t he semi- empirical and vapour pressure models t reat H
2
O as a
separat e phase using st eam t able correlat ions.
I n t hese correlat ions, H
2
O is assumed t o form an ideal, part ially-
miscible mixt ure wit h t he hydrocarbons and it s K value is comput ed
from t he r elat ionship:
where:
p = vapour pressure of H
2
O from St eam Tables
x
s
= solubilit y of H
2
O in hydrocarbon liquid at sat urat ion condit ions.
The value for x
s
is est imat ed by using t he solubilit y dat a for kerosene as
shown in Figure 9A1. 4 of t he API Dat a Book
19
. This approach is
generally adequat e when working wit h heavy hydrocarbon syst ems.
However, it is not recommended for gas syst ems.
For t hree phase syst ems, only t he PR and PRSV proper t y package and
Act ivit y Models allow component s ot her t han H
2
O in t he second liquid
phase. Special considerat ions are given when dealing wit h t he
solubilit ies of glycols and CH
3
OH. For acid gas syst ems, a t emperat ure
dependent int eract ion paramet er was used t o mat ch t he solubilit y of
t he acid component in t he wat er phase.
The PR equat ion considers t he solubilit y of hydrocarbons in H
2
O, but
t his value may be somewhat low. The reason for t his is t hat a
significant ly different int eract ion paramet er must be supplied for cubic
equat ions of st at e t o mat ch t he composit ion of hydrocarbons in t he
wat er phase as opposed t o t he H
2
O composit ion in t he hydrocarbon
phase. For t he PR equat ion of st at e, t he lat t er case was assumed more
crit ical. The second binary int eract ion paramet er in t he PRSV equat ion
allows for an improved solubilit y predict ion in t he alt ernat e phase.
Wit h t he act ivit y coefficient models, t he limit ed mut ual solubilit y of H
2
O
and hydrocarbons in each phase can be t aken int o account by
implement ing t he insolubilit y opt ion ( please refer t o Sect i on A. 3.2 -
(A.77) K
e
p
x
s
P ( )
--------- =
A- 71
Act i v i t y Model s) . UniSim Design generat es, upon request , int eract ion
paramet ers for each act ivit y model ( wit h t he except ion of t he Wilson
equat ion) t hat are fit t ed t o mat ch t he solubilit y of H
2
O in t he liquid
hydrocarbon phase and hydrocarbons in t he aqueous phase based on
t he solubilit y dat a referred t o in t hat sect ion.
The Peng- Robinson and SRK propert y packages will always force t he
wat er rich phase int o t he heavy liquid phase of a t hree phase st ream.
As such, t he aqueous phase is always forced out of t he bot t om of a
t hree phase separat or, even if a light liquid phase ( hydrocarbon rich)
does not exist . I n a t hree phase seperat or, solids are always carried in
t he second liquid phase.
A. 7. 7 Supercrit ical Handling
UniSim Design report s a vapor fract ion of zero or one, for a st r eam
under supercrit ical condit ions. Theoret ically, t his value doesn t have
any physical meaning for a supercrit cial fluid, since t here is no
dist inct ion of liquid or vapor phases in a supercrit ical region. However,
it is impor t ant t o det er mine if a supercrit ical fluid is liquid- like or a
vapor- like fluid. This is because some of t he propert ies report ed in
UniSim Design are calculat ed using cert ain set s of specific phase
models. I n ot her words, phase ident ificat ion has t o be carried out in
order t o decide which model t o use t o calculat e t hese propert ies.
I n UniSim Design, all flash result s go t hrough a phase order funct ion t o
ident ify t he phase t ype. Different packages have t heir own phase order
funct ion.
For example, t he following crit eria are used t o ident ify phase t ypes for
t he PR, SRK, SourPR, and Sour SRK cubic equat ions of st at e at
supercrit ical region:
1. I f t he compressibilit y fact or ( Z) is great er t han 0. 3, and t he
isot hermal compressibilit y fact or ( bet a) is great er t han 0. 75, a
vapor fract ion of 1. 0 is assigned t o t he st ream.
2. I f Z is great er t han 0. 75 and t he sum of composit ion of light
compounds ( NBP< 230K) is gr eat er t han t he sum of composit ion of
heavy compounds, a vapor fract ion of 1. 0 is assigned t o t he st ream.
Ot herwise, vapor fract ion of 0 is assigned t o t he st ream and liquid
correlat ions are used.
A- 72
A. 7. 8 Solids
UniSim Design does not check for solid phase format ion of pure
component s wit hin t he flash calculat ions, however, incipient solid
format ion condit ions for CO
2
and hydrat es can be predict ed wit h t he
Ut ilit y Package.
Solid mat erials such as cat alyst or coke can be handled as user- defined,
solid t ype component s. The UniSim Design propert y package t akes t his
t ype of component int o account in t he calculat ion of t he following
st ream variables: st ream t ot al flow rat e and composit ion ( molar, mass
and volume) , vapour fract ion, ent ropy, ent halpy, specific heat , densit y,
molecular weight , compressibilit y fact or, and t he various crit ical
propert ies. Transport propert ies are comput ed on a solids- free basis.
Solids do not part icipat e in vapour- liquid equilibrium ( VLE) calculat ions.
Their vapour pressure is t aken as zero. However, since solids do have
an ent halpy cont ribut ion, t hey have an effect on heat balance
calculat ions. Thus, while t he result s of a Temperat ure flash are t he
same whet her or not such component s are pr esent , an Ent halpy flash is
affect ed by t he presence of solids.
A solid mat erial component is ent ered as a hypot het ical component in
UniSim Design. See Chapt er 3 - Hy pot het i cal s for more informat ion
on Hypot het icals.
ut ilit ies, refer t o Chapt er
14 - Uni Si m Desi gn
Ut i l i t i es of t he Uni Si m
Desi gn Oper at i ons
Gui de.
A- 73
A. 7. 9 St ream I nformat ion
When a flash calculat ion occurs for a st ream, t he informat ion t hat is
ret urned depends on t he phases present wit hin t he st ream. The
following t able shows t he st ream propert ies t hat ar e calculat ed for each
phase:
St eam Pr oper t y Appl i cabl e Phases
A
Vapour Phase Mole Fract ion F V L S
Vapour Phase Mass Fract ion F V L S
Vapour Phase Volume Fract ion F V L S
Temperat ure F V L S
Pressure F V L S
Flow F V L S
Mass Flow F V L S
Liquid Volume Flow ( St d, I deal) F V L S
Volume Flow F V L S
St d. Gas Flow F V L S
St d. Volume Flow F L S
Energy F V L S
Molar Ent halpy F V L S
Mass Ent halpy F V L S
Molar Ent ropy F V L S
Mass Ent ropy F V L S
Molar Volume F V L S
Molar Densit y F V L S
Mass Densit y F V L S
St d. Liquid Mass Densit y F
D
L S
Molar Heat Capacit y F V L S
Mass Heat Capacit y F V L S
CP/ CV F V L S
Thermal Conduct ivit y F
B,D
V L
Viscosit y F
B,D
V L
Kinemat ic Viscosit y F
B,D
V L
Surface Tension F
B
L
Molecular Weight F V L S
Z Fact or F
B
V L S
Air SG F
B
V
Wat son ( UOP) K Value F V L S
Component Mole Fract ion F V L S
Component Mass Fract ion F V L S
Component Volume Fract ion F V L S
Component Molar Flow F V L S
Component Mass Flow F V L S
Component Volume Flow F V L S
K Value ( y/ x)
A
Stream phases:
F - Feed
V - Vapour
L - Liquid
S - Solid
A- 74
B
Physical property queries are allowed on the feed phase of single phase streams.
C
Physical property queries are allowed on the feed phase only for streams containing vapour and/or liquid
phases.
D
Physical property queries are allowed on the feed phase of liquid streams with more than one liquid phase.
Lower Heat ing Value
Mass Lower Heat ing Value
Molar Liquid Fract ion F V L S
Molar Light Liquid Fract ion F V L S
Molar Heavy Liquid Fract ion F V L S
Molar Heat of Vapourizat ion F
C
V L
Mass Heat of Vapourizat ion F
C
V L
Part ial Pressure of CO
2
F V L S
St eam Pr oper t y Appl i cabl e Phases
A
A- 75
A. 8 References
1
Peng, D. Y. and Robinson, D. B., "A Two Const ant Equat ion of St at e", I . E. C.
Fundament als, 15, pp. 59- 64 ( 1976) .
2
Soave, G., Chem Engr. Sci., 27, No. 6, p. 1197 ( 1972) .
3
Knapp, H., et al., "Vapor- Liquid Equilibria for Mixt ures of Low Boiling
Subst ances", Chemist ry Dat a Series Vol. VI , DECHEMA, 1989.
4
Kabadi, V.N., and Danner, R.P. A Modified Soave- Redlich- Kwong Equat ion of
St at e for Wat er- Hydrocarbon Phase Equilibria, I nd. Eng. Chem. Process
Des. Dev. 1985, Volume 24, No. 3, pp 537- 541.
5
St ryj ek, R., Vera, J.H., J. Can. Chem. Eng., 64, p. 334, April 1986.
6
API Publicat ion 955, A New Correlat ion of NH3, CO2 and H2S Volat ilit y Dat a
From Aqueous Sour Wat er Syst ems, March 1978.
7
Zudkevit ch, D., Joffee, J. "Correlat ion and Predict ion of Vapor- Liquid Equilibria
wit h t he Redlich- Kwong Equat ion of St at e", AI ChE Journal, Volume 16, No.
1, January pp. 112- 119.
8
Reid, C. R., Prausnit z, J. M. and Sherwood, T. K., "The Propert ies of Gases and
Liquids", McGraw- Hill Book Company, 1977.
9
Prausnit z, J.M., Licht ent haler, R. N., Azevedo, E. G., "Molecular
Thermodynamics of Fluid Phase Equilibria", 2nd. Ed., McGraw- Hill, I nc.
1986.
10
Chao, K. D. and Seader, J. D., A. I . Ch. E. Journal, pp. 598- 605, December
1961.
11
Grayson, H. G. and St reed, G. W., "Vapour- Liquid Equilibria for High
Temperat ure, High Pressure Syst ems", 6t h World Pet roleum Congress, West
Germany, June 1963.
12
Jacobsen, R. T and St ewart , R. B., 1973. "Thermodynamic Propert ies of
Nit rogen I ncluding Liquid and Vapour Phases from 63 K t o 2000K wit h
Pressure t o 10 000 Bar. " J. Phys. Chem. Reference Dat a, 2: 757- 790.
13
Hankinson, R.W. and Thompson, G.H., A.I . Ch. E. Journal, 25, No. 4, p. 653
( 1979) .
14
Ely, J. F. and Hanley, H. J.M., "A Comput er Program for t he Predict ion of
Viscosit y and Thermal Conduct ivit y in Hydrocarbon Mixt ures", NBS
Technical Not e 1039.
15
Twu, C.H., I . E. C. Proc Des & Dev, 24, p. 1287 ( 1985) .
16
Reid, R. C., Prausnit z, J.M., Poling, B. E., "The Propert ies of Gases & Liquids",
McGraw- Hill, I nc., 1987.
17
Woelflin, W., "Viscosit y of Crude- Oil Emulsions", present ed at t he spring
meet ing, Pacific Coast Dist rict , Division of Product ion, Los Angeles, Calif.,
Mar. 10, 1942.
18
Gambill, W.R., Chem. Eng., March 9, 1959.
19
API Technical Dat a Book, Pet roleum Refining, Fig. 9A1. 4, p. 9- 15, 5t h Edit ion
A- 76 Ref er ences
A- 76
( 1978) .
20
Keenan, J. H. and Keyes, F. G., Thermodynamic Propert ies of St eam, Wiley
and Sons ( 1959) .
21
Perry, R. H. ; Green, D. W.; Perrys Chemical Engineers Handbook Sixt h
Edit ion, McGraw- Hill I nc., ( 1984) .
22
Passut , C. A. ; Danner, R. P., Development of a Four- Paramet er
Corresponding St at es Met hod: Vapour Pressure Predict ion,
Thermodynamics - Dat a and Correlat ions, AI ChE Symposium Series; p. 30-
36, No. 140, Vol. 70.
23
M. Lencka and A. Anderko, AI ChE J. 39, 533( 1993)
24
M. Benedict , G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, ( 1940) , P.
334.
25
M. S. Han, and K. E. St arling , Thermo Dat a Refined for LPG. Part 14:
Mixt ures, Hydrocarbon Processing, Vol. 51, No. 5, ( 1972) , p. 129.
26
K. E. St arling, Fluid Thermodynamic Propert ies for Light Pet roleum Syst ems,
Gulf Publishing Co., Houst on, Texas ( 1973) .
27
Twu, C. H., et . al., "A New Generalized Alpha Funct ion for a Cubic Equat ion of
St at e: Part 1. Peng- Robinson Equat ion, " Fluid Phase Equilibria, 105, 49- 59
( 1995) .
28
Twu, C. H., et . al., "A New Generalized Alpha Funct ion for a Cubic Equat ion of
St at e: Part 2. Redlich- Kwong Equat ion, " Fluid Phase Equilibria, 105, 61- 69
( 1995) .
29
Twu, C. H., et . al., "An Ext ension of CEOS/ AE Zero- Pressure Mixing Rule for
An Opt imum Two- paramet er Cubic Equat ion of St at e, " I nd. Eng. Chem.
Res., 41, 931- 937 ( 2002) .
30
Twu, C. H., et . al., "A Versat ile Liquid Act ivit y Model for SRK, PR and A New
Cubic Equat ion of St at e TST," Fluid Phase Equilibria, 194- 197, 385- 399
( 2002)
31
Twu, C. H., et . al., "Get t ing a Handle on Advanced Cubic Equat ions of St at e" ,
Chemical Engineering Progress, Nov. 2002, 58- 65.
Oi l Met hods & Cor r el at i ons B- 1
B- 1
B Oil Met hods &
Correlat ions
B.1 I nt r oduct i on ............. ........................................................... .......... 2
B.2 Char act er i zat i on Met hod ...................................................... .......... 2
B.2.1 Generat e a Full Set of Working Curves . .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 3
B.2.2 Light Ends Analysis . .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
B.2.3 Aut o Calculat e Light Ends.. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 6
B.2.4 Det ermine TBP Cut point Temperat ures. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 6
B.2.5 Graphically Det ermine Component Propert ies . .. ... .. .. ... .. ... .. .. ... .. ... 7
B.2.6 Calculat e Component Crit ical Propert ies . ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
B.2.7 Correlat ions . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
B.3 Ref er ences ............... ........................................................... .......... 9
B- 2 I nt r oduct i on
B- 2
B. 1 I nt roduct ion
This appendix is a supplement t o Chapt er 4 - Uni Si m Desi gn Oi l
Manager . I ncluded in t his appendix is t he general procedure used by
UniSim Design t o charact erize an oil and a list of correlat ions used in
t he Oil Manager.
B. 2 Charact erizat ion Met hod
The procedure UniSim Design uses t o convert your assay dat a int o a
series of pet roleum hypocomponent s involves four maj or int ernal
charact erizat ion st eps:
1. Based on your input curves, UniSim Design calculat es a det ailed set
of full range Working Curves t hat include t he t rue boiling point ( TBP)
t emperat ure, molecular weight , densit y and viscosit y behaviour.
2. Next , by using eit her a default or user- supplied set of cut point
t emperat ures, t he corresponding fract ion for each hypocomponent
is det ermined from t he TBP working curve.
3. The normal boiling point ( NBP) , molecular weight , densit y and
viscosit y of each hypocomponent are graphically det ermined from
t he working curves.
4. For each hypocomponent , UniSim Design calculat es t he remaining
crit ical and physical pr opert ies from designat ed correlat ions, based
upon t he component ' s NBP, molecular weight , and densit y.
Knowledge of t he four phases of t he charact erizat ion process provides a
bet t er underst anding of how your input dat a influences t he final
out come of your charact erizat ion. The following sect ions det ail each
st ep of t he calculat ion.
B- 3
B. 2. 1 Generat e a Full Set of
Working Curves
To ensure accuracy, a t r ue boiling point ( TBP) curve and associat ed
molecular weight , densit y, and viscosit y pr opert y curves are required
for t he charact erizat ion calculat ions. UniSim Design t akes what ever
input curves you have supplied, and int erpolat es and ext rapolat es t hem
as necessary t o complet e t he range from 0 t o 100%. These full range
curves are referred t o as t he working curves.
I f you supply an ASTM D86, ASTM D1160, or EFV dist illat ion curve as
input , it is aut omat ically conver t ed t o a TBP dist illat ion curve. On t he
ot her hand, if you do not have any dist illat ion dat a, supplying t wo of
t he t hree bulk propert ies ( molecular weight , densit y, or Wat son ( UOP)
K fact or) allows UniSim Design t o calculat e an average
1
TBP dist illat ion
curve.
Physical propert y curves t hat were not supplied are calculat ed from
default correlat ions designed t o model a wide variet y of oils, including
condensat es, crude oils, pet r oleum fract ions, and coal- t ar liquids. I f you
supply a bulk molecular weight or bulk densit y, t he corresponding
physical pr opert y curve ( eit her user- supplied or generat ed) is
smoot hed and adj ust ed such t hat t he overall pr opert y is mat ched. A
t ypical TBP curve is illust rat ed below.
Fi gur e B.1
Default values of t he I BP
and FBP can be changed
on t he Boiling Ranges
view. Refer t o Sect i on
4. 4 - Oi l
Char act er i zat i on Vi ew .
Percent Dist illed 0 100
T
e
m
p
e
r
a
t
u
r
e
I BP
FBP
B- 4 Char act er i zat i on Met hod
B- 4
B. 2. 2 Light Ends Analysis
UniSim Design uses your Light Ends dat a t o eit her define or replace t he
low boiling port ion of your TBP, ASTM D86 or ASTM D1160 curve wit h
discret e pure component s. UniSim Design does not require t hat you
mat ch t he highest boiling point light - end wit h t he lowest boiling point
t emperat ure on t he TBP curve.
Using t he sample Light Ends analysis shown here, UniSim Design
replaces t he first port ion of t he TBP working curve t o t he assay
percent age j ust past t he boiling point of n- pent ane ( approximat ely 95F
or 36C) or 11. 3 vol% ( t he cumulat ive light ends t ot al) , whichever is
great er. The new TBP curve would include t he Light Ends Free port ion of
t he original sample beginning at 0% dist illed wit h t he associat ed I BP
represent ing t he remaining port ion of t he original sample.
Three possible Light Ends/ Assay sit uat ions can exist as depict ed in t he
next t hree figures. I n t he following figures:
Point A represent s t he boiling point of t he heaviest light - end, n-
Pent ane in t his example.
Point B represent s t he t emperat ure at which t he t ot al Light Ends
percent age int ersect s t he TBP working curve.
I f point s A and B coincide exact ly as shown in Fi gur e B. 2, UniSim
Design assigns t he TBP working curve' s I BP equal t o t he boiling point of
t he heaviest light end and normalizes t he remaining port ion of t he TBP
curve wit h t he light ends removed. All point s t hat lie below point B on
t he curve ar e eliminat ed.
Fi gur e B.2
T
e
m
p
e
r
a
t
u
r
e
I BP
FBP
NBP
nC
5
Port ion of Original Assay t hat will
be renormalized t o be on a Light
Ends Free Basis
Cumulat ive Light
Ends % Dist illed
A B
B- 5
Fi gur e B. 3 depict s t he sit uat ion t hat may arise from inconsist ent dat a
or fr om a poor ext rapolat ion of t he I BP. These sit uat ions are correct ed
by assuming t hat t he Light Ends analysis is cor rect and t hat t he error
exist s in t he int ernal TBP curve. I n t he figure, Point A ( boiling point of
t he heaviest light end component ) lies below Point B ( int ernal TBP
curve t emperat ure associat ed wit h your cumulat ive light ends
percent age) on t he int ernal TBP working curve. UniSim Design replaces
point B ( t he Light Ends free I BP) by a point t hat uses t he cumulat ive
light ends percent age and t he normal boiling point of t he heaviest light
ends component . The Light Ends free por t ion of t he curve is smoot hed
before normalizing.
Fi gur e B. 4 shows t he boiling point of t he heaviest light - end occurring
at an assay percent age great er t han t he cumulat ive Light Ends t ot al.
UniSim Design correct s t his sit uat ion by successively eliminat ing TBP
working curve point s from point B up t o t he first t emperat ure point
great er t han t he heaviest light end t emperat ure ( Point A) .
For example, if in t he above figure Point B represent s 5% and Point A
represent s 7%, t he new TBP curve ( which is light ends free) is
st ret ched, i. e., what was 93% of t he assay ( det ermined from point A) is
now 95% of t he assay. As in t he previous case, Point A' s t emperat ure is
Fi gur e B.3
Fi gur e B.4
T
e
m
p
e
r
a
t
u
r
e
I BP
FBP
NBP
nC
5
Port ion of Original Assay t hat will be
renormalized t o be on a Light Ends
Free Basis
Cumulat ive Light Ends % Dist illed
B
A
Percent Dist illed
0 100
T
e
m
p
e
r
a
t
u
r
e
I BP
FBP
NBP
nC
5
Port ion of Original Assay t hat
will be renormalized t o be on
a Light Ends Free Basis
Cumulat ive Light Ends % Dist illed
A
B
Port ion of TBP t hat is eliminat ed due t o
inconsist encies bet ween t he Dist illat ion
and Light - Ends Analyses
B- 6
assigned t o t he new TBP curves I BP, and t he Light Ends free port ion is
smoot hed and normalized.
B. 2. 3 Aut o Calculat e Light Ends
UniSim Design' Aut o Calculat e Light Ends procedure int ernally plot s t he
boiling point s of t he defined component s on t he TBP working curve and
det ermines t heir composit ions by int erpolat ion. UniSim Design adj ust s
t he t ot al Light Ends fract ion such t hat t he boiling point of t he heaviest
light end is at t he cent roid volume of t he last Light Ends component .
The figure below illust rat es t he Aut o Calculat e Light Ends removal
procedure.
B. 2. 4 Det ermine TBP Cut point
Temperat ures
You may specify t he hypocomponent breakdown by supplying a number
of cut point t emperat ures and t he corresponding number of cut s for
each t emperat ure range, or you may let UniSim Design calculat e an
opt imal set of cut point s for you based upon t he overall number of
hypocomponent you have designat ed. The charact erizat ion process
t hen uses it s TBP working curve and t he specified set of TBP cut point s
t o det ermine t he fract ion of each hypocomponent on t he input curve
basis.
I n Fi gur e B. 6, four component s are generat ed from t he TBP curve
using five TBP cut point s of equal t emperat ure incr ement . Refer t o
Fi gur e B.5
T
e
m
p
e
r
a
t
u
r
e
I BP
FBP
NBP nC
5
nC
4
iC
5
iC
4
0
100
iC
4
iC
5
nC
5
nC
4
Percent Dist illed
Cumulat ive
Light Ends
% Dist illed
Port ion of Original Assay t hat will be
Renormalized t o be on a Light Ends Free Basis
New I BP point for t he TBP curve
Cent roid Volume of t he Last
Light - End Component
B- 7
Sect i on 4. 6 - Hy pocomponent Gener at i on for more det ails.
B. 2. 5 Graphically Det ermine
Component Propert ies
Aft er t he cut point s and t he fract ion of each hypocomponent ar e known,
t he average boiling point may be det ermined. This is t he normal boiling
point ( NBP) , which is calculat ed for each component by equalizing t he
areas bet ween t he TBP curve and a horizont al line represent ing t he NBP
t emperat ure. This is shown in t he figure below, wit h t he grey areas
represent ing t he equalized areas. The average molecular weight ,
densit y, and viscosit y of each hypocomponent are subsequent ly
calculat ed fr om t he corresponding smoot hed working curves for
molecular weight , densit y and viscosit y.
Fi gur e B.6
Fi gur e B.7
T
e
m
p
e
r
a
t
u
r
e
T4
CUT1
CUT2 CUT3
CUT4
I BP
T3
T2
T1
T
e
m
p
e
r
a
t
u
r
e
T4
I BP
T3
T2
T1
Percent Dist illed
0
100
CUT1
CUT2 CUT3 CUT4
B- 8
B. 2. 6 Calculat e Component
Crit ical Propert ies
Knowing t he normal boiling point , molecular weight , and densit y
enables UniSim Design t o calculat e t he remaining physical and
t hermodynamic pr opert ies necessar y t o complet ely define t he
pet roleum hypocomponent . These propert ies are est imat ed for each
hypocomponent using default or user- select ed correlat ions as out lined
in Sect i on B. 2. 7 - Cor r el at i ons.
B. 2. 7 Correlat ions
The range of applicabilit y for t he crit ical propert y correlat ions are
explained below:
Cr i t i cal Pr oper t y
Cor r el at i on
Range of Appl i cabi l i t y
Lee- Kesl er These equat ions yield nearly ident ical result s t o t hose obt ained using t he
graphical correlat ions found in t he API Dat a Book for boiling t emperat ures
below 1250F ( 677C) . The equat ions are modified t o ext end beyond t his
range, but an upper limit is not given by t he aut hors.
Cavet t The aut hor does not present any reference as t o which dat a were used for
t he development of t he correlat ions or t heir limit at ions. Experience has
proven t hese correlat ions t o produce very good result s for fract ions whose
API gravit y is great er t han zero or for highly aromat ic and napht henic
fract ions such as coal t ar liquids.
Ri azi - Dauber t I n t he boiling point range 0 - 602F ( - 18 - 317C) , t hese correlat ions
perform slight ly bet t er t han ot her met hods. Their most serious drawback
is t he limit at ion of t he boiling point t o 855F ( 457C) for t he calculat ion of
crit ical pressure and molecular weight .
Nok ay Limit at ions for t hese correlat ions are not present ed in t he original
publicat ions. The crit ical t emperat ure and molecular weight correlat ions
are part icularly good for highly aromat ic or napht henic syst ems as shown
in a paper by Newman, " Correlat ions Evaluat ed for Coal Tar Liquids".
Roess The main limit at ion of t hese correlat ions is t hat t hey should not be used
for fract ions heavier t han C
20
( 650F, 343C) . They highly underest imat e
crit ical t emperat ures for heavier fract ions and should not be used for
heavy oil applicat ions.
Edmi st er These equat ions are very accurat e for pure component s, but are rest rict ed
t o condensat e syst ems wit h a limit ed amount of isomers. Edmist er
acent ric fact ors t end t o be lower t han Lee- Kesler values for fract ions
heavier t han C
20
( 650F, 343C) . I t is recommended t hat applicat ion of
t he Edmist er equat ion be rest rict ed t o t he range below C
20
.
Ber gman These correlat ions were developed for lean gases and gas condensat es
wit h relat ively light fract ions, t hereby limit ing t heir general applicabilit y t o
syst ems wit h carbon numbers less t han C
15
.
Spencer - Dauber t This family of correlat ions is a modificat ion of t he original Nokay equat ions
wit h a slight ly ext ended range of applicabilit y.
B- 9
B. 3 References
1
Whit son, C. H., Charact erizing Hydrocarbon Plus Fract ions, Societ y of
Pet roleum Engineers Journal, August 1983.
Row e These equat ions were present ed for est imat ing boiling point , crit ical
pressure and crit ical t emperat ure of paraffin hydrocarbons. Carbon
number, which is used as t he only correlat ing variable, limit s t he range of
applicabilit y t o light er paraffinic syst ems.
St andi ng The dat a of Mat t hews, Roland and Kat z was used t o develop t hese
correlat ions. Molecular weight and specific gravit y are t he correlat ing
variables. Alt hough St anding claims t he correlat ions are for C
7+
fract ions,
t hey appear t o be valid for narrower boiling point cut s as well. The
correlat ions should be used wit h caut ion for fract ions heavier t han C
25

( 841F, 450C) .
Ly der son
( Peng- Robi nson
PNA)
These correlat ions are based on t he PNA ( Paraffin/ Napt hene/ Aromat ic)
concept similar t o Peng- Robinson PNA. The met hod is limit ed t o
component s whose gravit y does not exceed 0.875 because of t he form of
t he PNA equat ions. Acent ric fact ors for fract ions heavier t han C
20
are
considerably higher t han t hose est imat ed from eit her t he Edmist er or Lee-
Kesler equat ion. These correlat ions are included primarily for
complet eness and should not be used for fluids cont aining fract ions
heavier t han C
20
Yar bor ough This met hod is only for use in t he predict ion of specific gravit y of
hydrocarbon component s. Carbon number and aromat icit y are t he
correlat ing variables for t his equat ion. The Yarborough met hod assumes
t hat t he C
7+
molecular weight and specific gravit y are measured. I t also
assumes t hat t he mole fract ions are measured from chromat ographic
analysis ( paraffin molecular weight s are assumed t o convert weight t o
mole fract ions) .
Kat z- Fi r oozabadi These correlat ions are only available for t he predict ion of molecular weight
and specific gravit y. Normal boiling point is t he only correlat ing variable
and applicat ion should be rest rict ed t o hydrocarbons less t han C
45
.
Mat hur Limit at ions for t hese correlat ions are not published by t he aut hor. These
equat ions produce excellent result s for highly aromat ic mixt ures such as
coal- t ar liquids, but are not rigorously examined for highly paraffinic
syst ems.
Penn St at e These correlat ions are similar t o Riazi- Daubert correlat ions and should
have approximat ely t he same limit at ions.
Honeyw el l These correlat ions yield result s quit e close t o t he Lee- Kesler equat ions,
but t end t o produce bet t er result s for aromat ic syst ems. Limit at ions for
t hese equat ions are not available, but t he Lee- Kesler limit at ions should
provide a good guide.
Har i u Sage These correlat ions were developed for est imat ing molecular weight from
boiling point and specific gravit y ut ilizing t he Wat son Charact erizat ion
Fact or, Kw. I t provides reasonable ext rapolat ion t o boiling point s great er
t han 1500F ( 816C) and is more accurat e t han t he Lee- Kesler molecular
weight correlat ion.
Cr i t i cal Pr oper t y
Cor r el at i on
Range of Appl i cabi l i t y
B- 10 Ref er ences
B- 10
Ami nes Pr oper t y Pack age C- 1
C- 1
C Amines Propert y
Package
C.1 Ami nes Pr oper t y Pack age .................................................... .......... 2
C.2 Non- Equi l i br i um St age Model ............................................... .......... 5
C.3 St age Ef f i ci ency ........ ........................................................... .......... 6
C.3.1 Non- Equilibrium St age Model .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
C.4 Equi l i br i um Sol ubi l i t y ........................................................... .......... 9
C.4.1 Kent & Eisenberg Model .. .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 9
C.4.2 Li- Mat her Elect rolyt e Model .. .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 12
C.5 Phase Ent hal py ......... ........................................................... .........17
C.6 Si mul at i on of Ami ne Pl ant Fl ow sheet s ................................. .........17
C.6.1 Solving t he Columns . .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 17
C.6.2 Converging t he Cont act or . ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 18
C.6.3 Converging t he Regenerat or . .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 19
C.6.4 Recycle Convergence. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 19
C.6.5 Operat ing Condit ions. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 19
C.7 Pr ogr am Li mi t at i ons . ........................................................... .........21
C.7.1 Range of Applicabilit y .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. .. 21
C.8 Ref er ences................ ........................................................... .........21
C- 2 Ami nes Pr oper t y Pack age
C- 2
C. 1 Amines Propert y Package
The removal of acid gases such as hydrogen sulphide ( H
2
S) and carbon
dioxide ( CO
2
) from process gas st reams is oft en required in nat ural gas
plant s and in oil refineries. There are many t reat ing processes
available. However, no single process is ideal for all applicat ions. The
init ial select ion of a part icular process may be based on feed
paramet ers such as composit ion, pressure, t emperat ure and t he nat ure
of t he impurit ies, as well as product specificat ions.
Final select ion is ult imat ely based on process economics, reliabilit y,
versat ilit y and environment al const raint s. Clearly t he select ion
procedure is not a t rivial mat t er and any t ool t hat provides a reliable
mechanism for pr ocess design is highly desirable.
Acid gas removal processes using absorpt ion t echnology and chemical
solvent s ar e popular, part icular ly t hose using aqueous solut ions of
alkanolamines. The Amines Propert y Package is a special propert y
package designed t o aid in t he modeling of alkanolamine t reat ing unit s
in which H2S and CO2 are removed fr om gas st reams. The Propert y
Package cont ains dat a t o model t he absorpt ion/ desorpt ion process
where aqueous solut ions of single amines - monoet hanolamine ( MEA) ,
diet hanolamine ( DEA) , met hyldiet hanolamine ( MDEA) , t riet hanolamine
( TEA) , 2, 2' - hydroxy- aminoet hylet her ( DGA) , or diisopropanolamine
( DI PA) and aqueous solut ions of blended amines - MEA/ MDEA, DEA/
MDEA or PZ/ MDEA ar e used.
The Ami nes Pr oper t y Pack age i s a speci al opt i on avai l abl e
f or Uni Si m Desi gn. For mor e i nf or mat i on on t hi s opt i on or
get i nf or mat i on on ot her Uni Si m Desi gn addi t i ons pl ease
cont act Honey w el l .
C- 3
Fi gur e C. 1 shows t he convent ional process configurat ion for a gas
t reat ing syst em t hat uses aqueous alkanolamine solut ions. The sour
gas feed is cont act ed wit h amine solut ion count er- current ly in a t rayed
or packed absorber. Acid gases are absorbed int o t he solvent t hat is
t hen heat ed and fed t o t he t op of t he regenerat ion t ower. St ripping
st eam produced by t he reboiler causes t he acid gases t o desorb from
t he amine solut ion as it passes down t he column. A condenser provides
reflux and t he acid gases are recovered overhead as a vapour product .
Lean amine solut ion is cooled and recycled back t o t he absorber. A
part ially st ripped, semi- lean amine st ream may be wit hdrawn from t he
regenerat or and fed t o t he absorber in t he split - flow modificat ion t o t he
convent ional plant flowsheet . A t hree- phase separat or or flash t ank
may be inst alled at t he out let of t he absorber t o permit t he recovery of
dissolved and ent rained hydrocarbons and t o reduce t he hydrocarbon
cont ent of t he acid gas product .
Fi gur e C. 1
C- 4 Ami nes Pr oper t y Pack age
C- 4
The design of amine t r eat ing unit s involves t he select ion of t he
following:
t he process configurat ion
t he amine t ype and concent rat ion
t he solut ion circulat ion rat e
t he reboiler heat requirement s
t he operat ing pressures and t emperat ures.
The mechanical t ray design and t he number of st ages in t he cont act or
are known t o affect t he pr ocess performance and are par t icularly
import ant in select ive absorpt ion applicat ions.
Amine t reat ing unit s were designed in t he past using hand calculat ions
and operat ing experience. Design condit ions were t ypically chosen
wit hin a conservat ive range t o cover t he deficiencies in t he dat a used in
t he hand calculat ions. Simulat ion is one means of obt aining values for
t he key design variables in t he process, and is generally used t o confirm
t he init ial design obt ained by t he above met hods.
Rules- of- t humb do not exist for t he design of select ive absorpt ion
applicat ions since operat ing experience is limit ed. Furt hermor e, t he
process is generally cont rolled by react ion kinet ics and cannot be
designed on t he basis of chemical equilibrium alone. The simulat ion
program must be relied upon as a predict ive t ool in t hese cases.
The AMSI M program uses t echnology developed by DB Robinson &
Associat es Lt d. t o model t he equilibrium solubilit y of acid gases in
aqueous amine solut ions.
A new nonequilibrium st age model which is based on t he st age
efficiency concept is used t o simulat e t he performance of cont act ors
and regenerat ors. A list of reference art icles on t he research leading t o
t he development of AMSI M can be found at t he end of t his sect ion. The
best dat a known t o exist is used t o det ermine t he component pr opert ies
in t he AMSI M dat abank.

Cur r ent l y Uni Si m Desi gn uses AMSI M ver si on 7.0. AMSI M
has al so been i nt egr at ed w i t h Uni Si mTher mo w hi ch uses
AMSI M ver si on 7. 3.
The AMSI M model s i s desi gned f or one ami ne or t w o ami nes.
When t w o ami nes ar e sel ect ed, t he Ami nes pr oper t y pack age
ex pect s bot h ami nes t o hav e a composi t i on or bot h ami nes
t o be zer o. You cannot speci f y one ami ne composi t i on t o be
gr eat er t han zer o and t he ot her t o be equal t o zer o. I t i s
suggest ed t hat i nst ead of speci f yi ng one ami ne t o be zer o,
i nput a v er y smal l composi t i on val ue f or sai d ami ne.
C- 5
C. 2 Non- Equilibrium St age
Model
A nonequilibrium st age model developed t o simulat e t he mult i-
component mult ist age mass t ransfer process encount ered in an amine
t reat ing unit is used in t he Amines Propert y Package.
The generalized st age model shown in Fi gur e C.2 gives t he flow
geomet ry and nomenclat ure for an individual st age in a column. The
fundament al concept used is t hat t he rat e of absorpt ion/ desorpt ion of
acid gases t o/ from t he amine solut ion must be considered as a
mass- t ransfer rat e process. This rat e process depends on t he
equilibrium and kinet ic paramet ers t hat describe t he acid gas/ amine
syst em.
The model incorporat es a modified Murphree- t ype vapour efficiency t o
account for t he varying mass- t ransfer rat es of individual acid gas
component s. The acid gas st age efficiencies are, in t urn, funct ions of
mass- t ransfer coefficient s and t he mechanical design of t he t ray.
When t he generalized st age model is ext ended t o t he mult ist age case,
t he result ing column flow geomet ry and nomenclat ure is shown in
Fi gur e C. 2. The result ing set of balance equat ions t hat charact erize
t he mult ist age unit are given in Sect i on C. 4 - Equi l i br i um Sol ubi l i t y .
This set of equat ions must be solved for each column in t he flowsheet .
A modified Newt on- Raphson met hod is used t o solve t he rigorous non-
linear st age equat ions simult aneously for t emperat ure, composit ion
C- 6 St age Ef f i ci ency
C- 6
and phase rat es on each st age in a column.
C. 3 St age Efficiency
The st age efficiency as defined under t he Amines propert y package
opt ion is given by:
where:
= St age efficiency
i = Component number
j = St age number
K = Equilibrium rat io
V = Molar flow rat e of vapour
X = Mole fract ion in liquid phase
Y = Mole fract ion in vapour phase
The st age efficiency is a funct ion of t he kinet ic rat e const ant s for t he
react ions bet ween each acid gas and t he amine, t he physico- chemical
propert ies of t he amine solut ion, t he pressure, t emperat ure and t he
mechanical t ray design variables such as t ray diamet er, weir height and
Fi gur e C. 2
( C. 1) q
V
j
SV
j
+ ( )Y
j
V
j 1 +
Y
ij 1 +
V
j
SV
j
+ ( )K
1j
X
ij
V
j 1 +
Y
ij 1 +
----------------------------------------------------- =
q
C- 7
weir lengt h.
You may specify t he st age efficiencies or have t hem calculat ed in
UniSim Design.
I f t he Ami nes opt i on i s sel ect ed, Uni Si m Desi gn al w ays uses
st age- component ef f i ci enci es. Not e t hat t he ef f i ci enci es used
ar e onl y f or H
2
S and C0
2
component s. I f t he ef f i ci enci es ar e
not speci f i ed f or t he col umn, Uni Si m Desi gn cal cul at es
ef f i ci enci es based on t he t r ay di mensi ons speci f i ed i n t he
Ami nes page of t he Col umn v i ew . I f no t r ay di mensi ons ar e
speci f i ed, Uni Si m Desi gn uses t he def aul t t r ay di mensi ons t o
cal cul at e t he st age ef f i ci enci es. These ar e r eal st ages, not
i deal st ages.
C- 8 St age Ef f i ci ency
C- 8
C. 3. 1 Non- Equilibrium St age
Model
Overall Mat erial Balance
Component Mat erial Balance
Energy Balance
Equilibrium Relat ionship
Summat ion Equat ion
( C. 2)
( C. 3)
( C. 4)
( C. 5)
( C. 6)
F
j
L
j 1
L
j
SL
j
+ ( ) V
j
SV
j
+ ( ) + 0 =
F
j
z
ij
L
j 1
x
ij 1
V
j 1 +
Y
ij 1 +
L
j
SL
j
+ ( )x
ij
V
j
SV
j
+ ( )y
ij
+ + 0 =
F
j
H
Fj
Q
j
L
j 1
h
j 1
V
j 1 +
H
j 1 +
L
j
SL
j
+ ( )h
j
V
j
SV
j
+ ( )H
i
+ + + 0 =
q
ij
K
ij
x
ij
V
j
SV
j
+ ( ) V
j
SV
j
+ ( )y
ij
1 q
ij
( )V
j 1 +
y
ij 1 +
+ 0 =
y
ij
1.0
0 =
C- 9
C. 4 Equilibrium Solubilit y
C. 4. 1 Kent & Eisenberg Model
A model based on t he Kent and Eisenberg approach is used t o correlat e
t he equilibrium solubilit y of acid gases in t he amine solut ions. The
reference art icles cont ain experiment al dat a t hat were used t o validat e
t he solubilit y model. Addit ional unpublished dat a for DEA, MDEA, MEA/
MDEA, and DEA/ MDEA syst ems have also been incorporat ed.
I mprovement s were made t o t he model t o ext end t he reliable range t o
mole loadings bet ween 0. 0001 and 1. 2. A propriet ary model was
developed t o predict t he solubilit y of acid gas mixt ures in t ert iary amine
solut ions. Solubilit ies of inert component s such as hydrocarbons are
modelled using a Henr y' s const ant adj ust ed for ionic st rengt h effect s.
The predict ion of equilibrium rat ios or K-values involves t he
simult aneous solut ion of a set of non- linear equat ions t hat describe t he
chemical and phase equilibria and t he elect roneut ralit y and mass
balance of t he elect rolyt es in t he aqueous phase. These equat ions are
provided below. The model is used t o int erpolat e and ext rapolat e t he
available experiment al solubilit y dat a in t he Amines Propert y Package.
For t ert iary amines t hat do not form carbamat e, t he equat ions involving
t hat ionic species are eliminat ed from t he model.
These equat ions are shown as follows:
Chemi cal React i ons
( C. 7)
( C. 8)
( C. 9)
(C.10)
(C.11)
(C.12)
R
1
R
2
NH H
2
O R
1
R
2
NH
2
+
OH
-
+ +
R
1
R
2
R
3
N H
2
O R
1
R
2
R
3
NH
+
OH
-
+ +
R
1
R
2
NH CO
2
R
1
R
2
NCOO
-
H
+
+ +
H
2
O H
+
OH
-
+
H
2
S H
+
HS
-
+
CO
2
H
2
O + H
+
HCO
3
-
+
C- 10 Equi l i br i um Sol ubi l i t y
C- 10

(C.13)
(C.14)
Equi l i br i um Rel at i ons
(C.15)
(C.16)
(C.17)
(C.18)
(C.19)
(C.20)
(C.21)
(C.22)
Phase Equi l i br i a
(C.23)
(C.24)
Char ge Bal ance
(C.25)
Chemi cal React i ons
HS
-
H
+
S
=
+
HCO
3
-
H
+
CO
3
=
+
K
1
H
+
| | R
1
R
2
NH | |
R
1
R
2
NH
2
+
| |
---------------------------- =
K
2
H
+
| | R
1
R
2
R
3
N | |
R
1
R
2
R
3
NH
+
| |
------------------------------ =
K
3
HCO
3
-
| | R
1
R
2
NH | |
R
1
R
2
NCOO
-
| |
----------------------------------- =
K
4
H
+
| | OH
-
| |
H
2
O | |
-------------------- =
K
5
H
+
| | HS
-
| |
H
2
S | |
------------------- =
K
6
H
+
| | HCO
3
-
| |
CO
2
| | H
2
O | |
------------------------ =
K
7
H
+
| | S
=
| |
HS
-
| |
----------------- =
K
8
H
+
| | CO
3
=
| |
HCO
3
-
| |
--------------------- =
y
H
2
S
|
H
2
S
V
P H
H
2
S
H
2
S | | =
y
CO
2
|
CO
2
V
P H
CO
2
CO
2
| | =
H
+
| | R
1
R
2
NH
2
+
| | R
1
R
2
R
3
NH
+
| | + +
OH
-
| | R
1
R
2
NCOO
-
| | HCO
3
-
| | HS
-
| | 2 CO
3
=
| | 2 S
=
| | + + + + +
=
C- 11
The fugacit y coefficient of t he molecular species is calculat ed by t he
Peng- Robinson equat ion of st at e:
where:
The t emperat ure- dependent quant it y o has t he following form.
The paramet ers o
1
and o
2
are subst ance- dependent and are
det ermined t hrough rigorous regr essions against reliable dat a.
For mixt ures, equat ion paramet ers a and b are est imat ed by t he
following mixing rules.
Mass Bal ance
(C.26)
(C.27)
(C.28)
(C.29)
(C.30)
(C.31)
(C.32)
(C.33)
(C.34)
(C.35)
C
1 2 amine ,
R
1
R
2
NH | | R
1
R
2
NH
2
+
| | R
1
R
2
NCOO
-
| | + + =
C
3 amine
R
1
R
2
R
3
N | | R
1
R
2
R
3
NH
+
| | + =
C
CO
2
C
1 2 amine ,
C
3 amine
+ ( )o
CO
2
CO
2
| | R
1
R
2
NCOO
-
| | HCO
3
-
| | CO
3
=
| | + + +
= =
C
H
2
S
C
1 2 amine ,
C
3 amine
+ ( )o
H
2
S
H
2
S | | HS
-
| | S
=
| | + +
= =
p
RT
v b
--------
a T ( )
v v b + ( ) b v b ( ) +
--------------------------------- =
a o 0.45724 ( )R
2
T
c
2
P
c
=
b 0.07780 ( )RT
c
P
c
=
o
1 2
1 o
1
1 T
r
( ) o
2
1 T
r
( ) 0.7 T
r
( ) + + =
a
i j
x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
( )

=
b
i j
x
i
x
j
b
i
b
j
+
2
-----------
\ .
| |
1 l
ij
( )

=
C- 12
C. 4. 2 Li- Mat her Elect rolyt e Model
The Amines pr opert y package is modified t o simulat e t hr ee phase
behaviour. For t he t hree phase simulat ion, t he K values from t he Peng-
Robinson pr opert y package were combined wit h t he K values from t he
Amines LLE and VLE package.
The Li- Mat her model shows a st rong predict ive capabilit y over a wide
range of t emperat ures, pressures, acid gas loadings, and amine
concent rat ions. AMSI M is capable of simulat ing processes wit h blended
solvent s made up of any t wo of six pr inciple amines ( MEA, DEA, MDEA,
TEA, DGA and DI PA) .
The framework of t he t hermodynamic model is based on t wo t ypes of
equilibria: vapour- liquid phase equilibria and liquidphase chemical
equilibria.
Phase Equilibria
The vapour- liquid equilibria of t he molecular species is given by:
where:
Hi = Henrys const ant
x
i
, y
i
= mole fract ion of molecular species i in t he liquid and gas phase
= fugacit y coefficient in t he gas phase
= act ivit y coefficient in t he liquid phase
The fugacit y coefficient is calculat ed by t he Peng- Robinson equat ion of
st at e ( Peng and Robinson, 1976) :
Where t he paramet ers are obt ained from t he EQUI - PHASE EQUI 90
TM

program library. The act ivit y coefficient is calculat ed by t he Clegg- Pit zer
equat ion t hat is described lat er in t his sect ion.
(C.36)
(C.37)
y
i
u
i
V
P H
i
x
i
i
L
=
u
i
V
i
L
P
RT
V b
---------
a T ( )
V V b + ( ) b V b ( ) +
------------------------------------ =
C- 13
Chemical Equilibria
I n case of single amine- H
2
S- CO
2
- H
2
O syst ems, t he import ant chemical
dissociat ion react ions are as follows:
The chemical equilibrium const ant s in t he acid gas - amine syst ems
play an import ant role in t he predict ion of t he equilibrium solubilit ies of
acid gases in t he aqueous amine solut ions. The equilibrium const ant K
can be expressed by:
The equilibrium const ant is expressed as a funct ion of t emperat ure:
Henrys const ant has t he same funct ion of t emperat ure as t hat in
equat ion ( C. 45) . I n t he liquid phase, t here ar e four molecular species,
Amine, H
2
O, CO
2
, H
2
S and seven ionic species, Amine
+
, HCO
3
-
, HS
-
,
H
+
, OH
-
, CO
3
=
, S
=
for t he amine- H
2
S- CO
2
- H
2
O syst em. I n t he gas
phase, t here are only four molecular species, Amine, H
2
O, CO
2
and
H
2
S.
The det erminat ion of t he composit ions of all molecular and ionic species
in bot h vapour and liquid phases involves t he simult aneous solut ion of a
set of non- linear equat ions t hat describe t he phase equilibria and
chemical equilibria, elect roneut ralit y ( charge balance) and mass
balance of t he elect rolyt es in t he aqueous solut ion.
Chemi cal Di ssoci at i on React i ons
( C. 38)
( C. 39)
( C. 40)
( C. 41)
( C. 42)
( C. 43)
(C.44)
(C.45)
Amine
+
Amine H
+
+
H
2
S HS
-
H
+
+
CO
2
H
2
O HCO
3
-
H
+
+ +
H
2
O OH
-
H
+
+
HCO
3
-
CO
3
=
H
+
+
HS
-
S
=
H
+
+
K H
i
x
i
y
i
( )
|
i
=
K ln C
1
C
2
T C
3
T C
4
T + ln + + =
C- 14
The Clegg- Pit zer Equat ion
The original Pit zer equat ion ( Pit zer, 1973) did not consider t he solvent
molecules in t he syst em as int eract ing part icles. Thus it is not suit able
for t he t hermodynamic descript ion of t he mixed- solvent syst ems. I n t he
Clegg- Pit zer model, all t he species in t he syst em were considered as
int eract ing part icles. The long- range elect rost at ic t erm and t he short -
range hard- sphere- repulsive t erm deduced from t he McMillan- Mayer' s
st at ist ical osmot ic- pressure t heory remained unchanged. The excess
Gibbs free energy, g
ex
consist s of t he long- range Debye- Huckel
elect rost at ic int eract ion t erm, g
DH
and t he short - range Margules
expansions wit h t wo- and t hree- suffix, g
s
:
where:

The expressions of act ivit y coefficient for solvent N and ion M
+
are as
(C.46)
(C.47)
(C.48)
g
ex
g
DH
g
s
+ =
g
DH
RT
-------
4A
x
I
x
---------- 1 I
x
1 2
+ ( ) x
c
x
a
B
ac
g oI
x
1 2
( )
a
+ ln =
g
s
RT
----- a
ij
x
i
x
j
a
ijk
x
i
x
j
x
k
k
+
a
=
g
s
RT
----- x
I
x
n
F
c
F
a
W
nca
x
n
x
n'
A
nn'
x
n'
A
n' n
x
n
+ ( )
n
""
+
a
=
A
nn'
2a
nn'
3a
n' n
+ =
A
nn'
2a
nn'
3a
nn' n' '
+ =
W
nca
2w
nc
2w
na
w
ca
2u
nc
2u
na
+ + + ( ) 4 =
w
ij
2a
ij
3 2 a
iij
a
ijj
+ ( ) + =
u
ij
3 2 a
iij
a
ijj
( ) =
C- 15
follows:
Where subscript s c, a, n and n represent cat ion, anion and molecular
species, respect ively. The subscript 2 in equat ion ( C. 50) st ands for
wat er. t he t ot al mole fract ion of ions ( x
I
) is given by:
The cat ion and anion fract ions Fc and Fa are defined for fully
symmet rical elect rolyt e syst ems by
The mole fract ion ionic st rengt h I
x
is defined as
(C.49)
(C.50)
(C.51)
(C.52)
(C.53)
(C.54)
N
ln
2A
x
I
x
3 2
1 I
x
1 2
+
---------------- x
c
x
a
B
ca
oI
x
1 2
( ) x
I
1 x
N
( ) F
c
F
a
W
Nca
x
I
'x
n
F
c
F
a
W
nca
'x
n
A
Nn
x
n
1 2x
N
( ) 2A
nN
x
N
1 x
N
( ) + | |
2 ' 'x
n
x
n'
A
nn'
x
n'
A
n' n
x
n
+ ( )
n'
+
a
+ exp
a
M
+
ln z
M
2
A
x
2
-- 1 I
x
1 2
+ ( )
I
x
1 2
1 2I
x
z
M
2
( )
1 I
x
1 2
+
------------------------------- + ln x
a
B
ma
g oI
x
1 2
( )
x
c
x
a
B
ca
z
M
2
g oI
x
1 2
( )
2I
x
--------------------- 1 z
M
2
2I
x
( ) oI
x
1 2
( ) exp + 2 x
n
F
a
W
nMa
x
n
1 x
I
+ ( ) F
c
F
a
W
nca
2 F
a
W
2Ma
F
c
F
a
W
2ca
2 x
n
x
n'
A
nn'
x
n'
A
n' n
x
n
+ ( )
n'
+
a
+
a
+ =
x
I
1 x
n
=
F
c
2x
c
x
I
=
F
a
2x
a
x
I
=
I
x
1 2 z
i
2
x
I
=
C- 16
The funct ion of g( x) is expressed by
where:
A
x
is t he Debye- Huckel paramet er on a mole fract ion basis:
where:
C
i
, C
n
= molar concent rat ions of t he ion i and solvent n, respect ively
I = ionic st rengt h in molar concent rat ion
= Debye- Huckel paramet er, which is a funct ion of t emperat ure,
densit y and dielect ric const ant of t he mixed solvent s
= relat ed t o t he hard- core collision diamet er, or dist ance of closest
approach bet ween ions in solut ion
A
n' n
and A
nn'
= int eract ion paramet ers bet ween and among t he
molecular species, respect ively
B
ca
= hard sphere repulsion paramet er bet ween ions
W
nca
= t he int eract ion paramet er bet ween ions and bet ween ion and
solvent
Paramet ers A
n' n
, A
nn'
, B
ca
and W
nca
share t he same funct ion of
t emperat ure:
The Clegg- Pit zer equat ions appear t o be uncompromisingly long and
cont ain many t er ms and paramet ers. However, it should be point ed out
t hat only a few paramet ers were used and many t erms, such as t he
quat ernary t erms in t he original Clegg- Pit zer equat ions were omit t ed in
t his model. I t can be seen t hat only A
nn'
, A
n' n
, B
ca
and W
nca
appear in
t he expressions and are t reat ed as adj ust able paramet ers.
(C.55)
(C.56)
(C.57)
g x ( ) 2 1 1 x + ( ) x ( ) exp | | x
2
=
x oI
x
1 2
2I
1 2
= =
I 1 2 z
i
2
C
i
=
A
x
A
|
C
n
( )
1 2
=
A
|
Y a b T + =
C- 17
I n t his model, bot h wat er and amine are t r eat ed as solvent s. The
st andard st at e of each solvent is t he pure liquid at t he syst em
t emperat ure and pressure. The adopt ed reference st at e for ionic and
molecular species is t he ideal and infinit ely dilut e aqueous solut ion.
C. 5 Phase Ent halpy
Vapour phase ent halpy is calculat ed by t he Peng- Robinson equat ion- of-
st at e which int egrat es ideal gas heat capacit y dat a from a reference
t emperat ure. Liquid phase ent halpy also includes t he effect of lat ent
heat of vaporizat ion and heat of react ion.
The absorpt ion or desorpt ion of H2S and CO2 in aqueous solut ions of
alkanolamine involves a heat effect due t o t he chemical react ion. This
heat effect is a funct ion of amine t ype and concent rat ion, and t he mole
loadings of acid gases. The heat of solut ion of acid gases is obt ained by
different iat ing t he experiment al solubilit y dat a using a form of t he
Gibbs- Helmholt z equat ion.
The heat effect which result s from evaporat ion and condensat ion of
amine and wat er in bot h t he absorber and regenerat or is account ed for
t hrough t he lat ent heat t erm which appears in t he calculat ion of liquid
ent halpy. Wat er cont ent of t he sour gas feed can have a dramat ic effect
on t he predict ed t emperat ure profile in t he absorber and should be
considered, part icular ly at low pressures.
C. 6 Simulat ion of Amine Plant
Flowsheet s
The key t o solving an amine t r eat ing syst em lies in t he simulat ion of
t he cont act or and t he regenerat or. I n bot h columns, rigorous non-
equilibrium st age efficiency calculat ions are used. I n addit ion, t he
cont act or efficiency incorporat es kinet ic react ion and mass t ransfer
paramet ers. Only t he Amines Propert y Package can effect ively simulat e
t his syst em, and only component s included in t his package should be
used.
C. 6. 1 Solving t he Columns
Follow t hese general guidelines:
Ensure t hat t he gas t o t he Cont act or is sat urat ed wit h wat er.
Use act ual, not ideal, st ages.
C- 18 Si mul at i on of Ami ne Pl ant
C- 18
Change st age efficiencies for CO2 and H2S from t heir default
values of 1. 0 t o fract ions for t he regenerat or and t he init ial
absorber run.
Use calculat ed efficiencies for subsequent absorber runs as
det ailed below.
Change t he damping fact or from a default value of 1. 0 t o a
fract ion as recommended in t he following sect ion. This may be
necessar y t o prevent oscillat ion during convergence.
C. 6. 2 Converging t he Cont act or
Convergence is most readily achieved by first solving wit h est imat ed
efficiencies ( suggest ed values are 0. 3 for CO2 and 0. 6 for H2S) , t hen
request ing calculat ed efficiencies and rest art ing t he column. To do t his,
you must first specify t hree dimensions for each t ray: t ray diamet er,
weir lengt h and weir height . Specify t hese paramet ers in t he Amines
page of t he Paramet ers t ab in t he Column view.
For an exist ing column, use t he act ual dimensions. For a design
sit uat ion ( or when t he t ray dimensions are unknown) use t he Tray
Sizing ut ilit y t o est imat e t hese paramet ers. I nput t he calculat ed t ray
dimensions and select Run. UniSim Design will calculat e t he individual
component efficiencies ( H
2
S, CO
2
) based on t he t ray dimensions. Only
single pass t rays can be modeled wit h t he Amines Propert y Package. I f
t he t rays in your column are mult ipass, you must est imat e t he
dimensions based on a single pass t ray.
Aft er t he t ray dimensions are specified, t he column is recalculat ed. Not e
t hat efficiencies can be calculat ed only when using t he Amines Propert y
Package. These values apply specifically t o CO2 and H2S. Damping
fact ors in t he range 0. 4 - 0. 8 usually give t he fast est convergence.
Temperat ur es ar ound t he cont act or should be as follows:
Cont act or St r eam Temper at ur e Range
Feed Gas 65 - 130 F
Lean MEA, DEA, TEA, MDEA 100 - 120 F
Lean DGA 140 F
( lean amine minimum 10 F > feed gas)
Absor ber Bot t oms 120 - 160 F
C- 19
C. 6. 3 Converging t he Regenerat or
As wit h t he Cont act or, efficiencies can be eit her specified by t he user, or
calculat ed by t he program. For t he condenser and reboiler, values of
1. 0 must be used. For t he remaining t rays, efficiencies of 0. 15 for CO2
and 0. 80 for H2S are suggest ed init ial est imat es.
The easiest specificat ions t o converge are t he st age 1 ( condenser)
t emperat ure and t he reboiler dut y. Following is a guideline for t ypical
dut ies.
The reboiler t emperat ure should not exceed 280 F t o avoid physical
degradat ion of t he amines int o corrosive by- product s. Regenerat ors
usually converge best wit h reflux rat io est imat es of 0. 5 - 3. 0 and
damping fact ors of 0. 2 - 0. 5.
C. 6. 4 Recycle Convergence
The remaining unit operat ions in t he flowsheet are st raight forward.
Not e t hat you need a wat er makeup st ream, as indicat ed in Fi gur e
C. 1. Since t he lean amine concent rat ion may vary due t o wat er
carryover in t he product from t he vessels, a wat er makeup is required
t o maint ain a desired concent rat ion.
Amine losses in t he cont act or overhead are usually negligible and t he
makeup st ream replaces any wat er lost so t he amine concent rat ion in
t he recycle does not change significant ly during t he recycle
convergence. Thus, you can quit e easily make an excellent init ial
est imat e for t he lean amine recycle. The phase, of course, is liquid and
t he t emperat ure, pressure, t ot al flow rat e and composit ion are known.
Alt hough t he composit ion of CO2 and H2S is unknown, t hese sour
component s have only a very minor impact on t he recycle and can
init ially be specified t o be zero in t he recycle st ream.
C. 6. 5 Operat ing Condit ions
The Amines pr opert y package cont ains dat a for t he following
Ami ne Dut y , BTU/ US Gal l on
TEA, MDEA 800
DEA 1,000
MEA 1,200
DGA 1,300
C- 20 Si mul at i on of Ami ne Pl ant
C- 20
alkanolamines and mixt ures of alkanolamines.
Many differ ent amine syst em designs can be modelled. However, for
bot h good t ower convergence and opt imum plant operat ion, t he
following guidelines are recommended:
* Amine mixt ures are assumed t o be primarily MDEA.
Ami ne
Uni Si m Desi gn
Name
Monoet hanol ami ne MEA
Di et hanol ami ne DEA
Tr i et hanol ami ne TEA
Met hy l di et hanol ami ne MDEA
Di gl y col ami ne DGA
Di i sopr opanol ami ne DI PA
Monoet hanol ami ne/ Met hyl di et hanol ami ne Bl end MEA/ MDEA
Di et hanol ami ne/ Met hl y di et hanol ami ne Bl end DEA/ MDEA
Ami ne
Lean Ami ne
St r engt h
Max i mum Aci d Gas Loadi ng
( Mol es Aci d Gas/ Mol e Ami ne)
Wei ght % CO2 H2S
MEA 15 - 20 0.50 0.35
DEA 25 - 35 0.45 0.30
TEA, MDEA 35 - 50 0.30 0.20
DGA 45 - 65 0.50 0.35
DEA/ MDEA* 35 - 50 0.45 0.30
MEA/ MDEA* 35 - 50 0.45 0.30
C- 21
C. 7 Program Limit at ions
The Amines pr opert y package cont ains correlat ions of dat a which
rest rict it s use t o cert ain condit ions of pressure, t emperat ure and
composit ion. These limit at ions ar e given below.
The chemical and physical propert y dat a base is rest rict ed t o amines
and t he following component s:
C. 7. 1 Range of Applicabilit y
The following t able displays t he equilibrium solubilit y limit at ions t hat
should be observed when using t his propert y package.
C. 8 References
1
At wood, K., M. R. Arnold and R. C. Kindrick, "Equilibria for t he Syst em,
Et hanolamines- Hydrogen Sulfide-Wat er", I nd. Eng. Chem., 49, 1439- 1444,
1957.
Av ai l abl e Component s w i t h Ami nes Pr oper t y Pack age
Aci d Gases CO2, H2S, COS, CS2
Hy dr ocar bons CH4 t o C12
Ol ef i ns C2= , C3= , C4= , C5=
Mer capt ans M- Mercapt an, E- Mercapt an
Non- Hydr ocar bons H2, N2, O2, CO, H2O
Ar omat i c C6H6, Toluene, e- C6h6, m-Xylene
Thi s met hod does not al l ow f or t he use of any hypot het i cal s.
Ami ne
Al k anol ami ne
Concent r at i on
Aci d Gas Par t i al
Pr essur e
Temper at ur e
Range ( Wt % ) psi a
o
F
MEA 0 - 30 0. 00001 - 300 77 - 260
DEA 0 - 50 0. 00001 - 300 77 - 260
TEA 0 - 50 0. 00001 - 300 77 - 260
MDEA 0 - 50 0. 00001 - 300 77 - 260
DGA 50 - 70 0. 00001 - 300 77 - 260
DI PA 0 - 40 0. 00001 - 300 77 - 260
For ami ne mi x t ur es, use t he val ues f or MDEA ( assumed t o be
t he pr i mar y ami ne) .
C- 22 Ref er ences
C- 22
2
Aust gen, D. M., G. T. Rochelle and C.- C. Chen, "Model of Vapour- Liquid
Equilibria for Aqueous Acid Gas Alkanolamine Syst ems", I nd. Eng. Chem.
Res., 03, 543- 555, 1991.
3
Bosch, H., "Gas- Liquid Mass Transfer wit h Parallel Reversible React ions- I I I .
Absorpt ion of CO2 int o Solut ions of Blends of Amines", Chem. Eng. Sci., 44,
2745- 2750, 1989.
4
Chakravart y, T., "Solubilit y Calculat ions for Acid Gases in Amine Blends",
Ph. D. Dissert at ion, Clarkson College, Pot sdam, NY, 1985.
5
Danckwert s, P. V., and M.M. Sharma, "The Absorpt ion of Carbon Dioxide int o
Solut ions of Alkalis and Amines", The Chemical Engineer, No. 202, CE244-
CE279, 1966.
6
Deshmukh, R. D. and A. E. Mat her, "A Mat hemat ical Model for Equilibrium
Solubilit y of Hydrogen Sulfide and Carbon Dioxide in Aqueous Alkanolamine
Solut ions",
7
Chem. Eng. Sci., 36, 355- 362, 1981.
8
Dingman, J. C., "How Acid Gas Loadings Affect Physical Propert ies of MEA
Solut ions", Pet . Refiner, 42, No. 9, 189- 191, 1963.
9
Dow Chemical Company, "Alkanolamines Handbook", Dow Chemical
I nt ernat ional, 1964.
10
I saacs, E. E., F. D. Ot t o and A. E. Mat her, "Solubilit y of Mixt ures of H2S and CO2
in a Monoet hanolamine Solut ion at Low Part ial Pressures", J. Chem. Eng.
Dat a, 25, 118- 120, 1980.
11
Jou, F.-Y., A. E. Mat her, and F.D. Ot t o, "Solubilit y of H2S and CO2 in Aqueous
Met hyldiet hanolamine Solut ions", I nd. Eng. Chem. Process Des. Dev., 21,
539- 544, 1982.
12
Jou, F.-Y., F. D. Ot t o and A. E. Mat her, Solubilit y of H2S and CO2 in
Triet hanolamine Solut ions, Present ed at t he AI ChE Wint er Nat ional
Meet ing, At lant a, Georgia, March 11- 14, 1984.
13
Jou, F.-Y., F. D. Ot t o and A. E. Mat her, "Solubilit y of Mixt ures of H2S and CO2 in
a Met hyldiet hanolamine Solut ion", Paper 140b, Present ed at t he AI ChE
Annual Meet ing, Miami Beach, Florida, Nov. 2- 7, 1986.
C- 23
14
Jou, F.-Y., A. E. Mat her and F. D. Ot t o, "The Solubilit y of Mixt ures of Hydrogen
Sulfide and Carbon Dioxide in Aqueous Met hyldiet hanolamine Solut ions",
Submit t ed t o The Canadian Journal of Chemical Engineering, 1992.
15
Kahrim, A. and A. E. Mat her, "Ent halpy of Solut ion of Acid Gases in DEA
Solut ions", Present ed at t he 69t h AI ChE Annual Meet ing, Chicago, I llinois,
Nov. 28- Dec. 2, 1976.
16
Kat z, D. L., D. Cornell, R. Kobayashi, F.H. Poet t mann, J. A. Vary, J. R. Elenbaas
and C. F. Weinaug, "Handbook of Nat ural Gas Engineering", McGraw- Hill,
New York, 1959.
17
Kent , R. L., and B. Eisenberg, "Bet t er Dat a for Amine Treat ing", Hydrocarbon
Processing, 55, No. 2, 87- 90, 1976.
18
Kohl, A.L. and F. C. Riesenfeld, "Gas Purificat ion", 4t h Ed., Gulf Publishing Co.,
Houst on, Texas, 1985.
19
Lal, D., E. E. I saacs, A. E. Mat her and F.D. Ot t o, "Equilibrium Solubilit y of Acid
Gases in Diet hanolamine and Monoet hanolamine Solut ions at Low Part ial
Pressures", Proceedings of t he 30t h Annual Gas Condit ioning Conference,
Norman, Oklahoma, March 3- 5, 1980.
20
Lawson, J. D., and A. W. Garst , "Gas Sweet ening Dat a: Equilibrium Solubilit y of
Hydrogen Sulfide and Carbon Dioxide in Aqueous Monoet hanolamine and
Aqueous Diet hanolamine Solut ions", J. Chem. Eng. Dat a, 21, 20- 30,
1976.
21
Lawson, J.D., and A. W. Garst , "Hydrocarbon Gas Solubilit y in Sweet ening
Solut ions: Met hane and Et hane in Aqueous Monoet hanolamine and
Diet hanolamine", J. Chem Eng. Dat a, 21, 30- 32, 1976.
22
Lee, J. I ., F.D. Ot t o, and A. E. Mat her, "Solubilit y of Carbon Dioxide in Aqueous
Diet hanolamine Solut ions at High Pressures", J. Chem. Eng. Dat a, 17, 465-
468, 1972.
23
Lee, J.I ., F. D. Ot t o, and A. E. Mat her, "Solubilit y of Hydrogen Sulfide in
Aqueous Diet hanolamine Solut ions at High Pressures", J. Chem. Eng. Dat a,
18, 71- 73, 1973a.
24
Lee, J.I ., F. D. Ot t o, and A.E. Mat her, "Part ial Pressures of Hydrogen Sulfide
over Aqueous Diet hanolamine Solut ions", J. Chem. Eng. Dat a, 18, 420,
1973b.
25
Lee, J.I ., F. D. Ot t o, and A. E. Mat her, "The Solubilit y of Mixt ures of Carbon
Dioxide and Hydrogen Sulphide in Aqueous Diet hanolamine Solut ions",
Can. J. Chem. Eng., 52, 125- 127, 1974a.
26
Lee, J.I ., F. D. Ot t o and A. E. Mat her, "The Solubilit y of H2S and CO2 in
Aqueous Monoet hanolamine Solut ions", Can. J. Chem. Eng., 52, 803- 805,
1974b.
27
Lee, J.I ., F. D. Ot t o and A. E. Mat her, "Solubilit y of Mixt ures of Carbon Dioxide
and Hydrogen Sulfide in 5. 0 N Monoet hanolamine Solut ion", J. Chem. Eng.
Dat a, 20, 161- 163, 1975.
28
Lee, J.I ., F. D. Ot t o and A. E. Mat her, "Equilibrium in Hydrogen Sulfide-
Monoet hanolamine-Wat er Syst em", J.Chem. Eng. Dat a, 21, 207- 208,
1976a.
C- 24 Ref er ences
C- 24
29
Lee, J.I ., F. D. Ot t o and A. E. Mat her, "The Measurement and Predict ion of t he
Solubilit y of Mixt ures of Carbon Dioxide and Hydrogen Sulphide in a 2. 5 N
30
Monoet hanolamine Solut ion", Can. J. Chem. Eng., 54, 214- 219, 1976b.
31
Lee, J. I ., F.D. Ot t o and A. E. Mat her, "Equilibrium Bet ween Carbon Dioxide and
Aqueous Monoet hanolamine Solut ions", J. Appl. Chem. Biot echnol., 26,
32
541- 549, 1976c.
33
Lee, J.I . and A. E. Mat her, "Solubilit y of Hydrogen Sulfide in Wat er", Ber.
Bunsenges z. Phys. Chem., 81, 1020- 1023, 1977.
34
Mason, D. M. and R. Kao, "Correlat ion of Vapor- Liquid Equilibria of Aqueous
Condensat es from Coal Processing" in Thermodynamics of Aqueous
Syst ems wit h I ndust rial Applicat ions, S. A. Newman, ed., ACS Symp. Ser.,
133, 107- 139, 1980.
35
Murzin, V.I ., and I . L. Leit es, "Part ial Pressure of Carbon Dioxide Over I t s
Dilut e Solut ions in Aqueous Aminoet hanol", Russian J. Phys. Chem., 45,
230- 231, 1971.
36
Nasir, P. and A. E. Mat her, "The Measurement and Predict ion of t he Solubilit y of
Acid Gases in. Monoet hanolamine Solut ions at Low Part ial Pressures", Can.
J. Chem. Eng., 55, 715- 717, 1977.
37
Ot t o, F.D., A. E. Mat her, F.-Y. Jou, and D. Lal, "Solubilit y of Light Hydrocarbons
in Gas Treat ing Solut ions", Present ed at t he AI ChE Annual Meet ing, Paper
21b, San Francisco, California, November 25- 30, 1984.
38
Peng, D.-Y., and D.B. Robinson, "A New Two- Const ant Equat ion of St at e", I nd.
Eng. Chem. Fundam., 15, 59- 64, 1976.
39
Rangwala, H. A., B. R. Morrell, A. E. Mat her and F. D. Ot t o, "Absorpt ion of CO2
int o Aqueous Tert iary Amine/ MEA Solut ions", The Canadian Journal of
Chemical Engineering, 70, 482- 490, 1992.
40
Tomcej , R. A. and F. D. Ot t o, "Comput er Simulat ion and Design of Amine
Treat ing Unit s", Present ed at t he 32nd Canadian Chemical Engineering
Conference, Vancouver, Brit ish Columbia, Oct . 3- 6, 1982.
41
Tomcej , R. A., F.D. Ot t o and F. W. Nolt e, "Comput er Simulat ion of Amine
Treat ing Unit s", Present ed at t he 33rd Annual Gas Condit ioning Conference,
Norman,
42
Oklahoma, March 7- 9, 1983.
43
Tomcej , R. A., "Simulat ion of Amine Treat ing Unit s Using Personal Comput ers",
Present ed at t he 35t h Canadian Chemical Engineering Conference, Calgary,
Albert a, Oct . 5- 8, 1985.
44
Tomcej , R. A. and F. D. Ot t o, "I mproved Design of Amine Treat ing Unit s by
Simulat ion using Personal Comput ers", Present ed at t he World Congress I I I
of Chemical Engineering, Tokyo, Japan, Sept ember 21- 25, 1986.
45
Tomcej , R. A., D. Lal, H. A. Rangwala and F. D. Ot t o, "Absorpt ion of Carbon
Dioxide int o Aqueous Solut ions of Met hyldiet hanolamine", Present ed at t he
AI ChE Annual Meet ing, Miami Beach, Florida, Nov. 2- 7, 1986.
46
Tomcej , R. A., F.D. Ot t o, H.A. Rangwala and B. R. Morrell, "Tray Design for
Select ive Absorpt ion", Present ed at t he 37t h Annual Laurance Reid Gas
C- 25
Condit ioning Conference, Norman, Oklahoma, March 2- 4, 1987.
47
Union Carbide Corporat ion, "Gas Treat ing Chemicals", Union Carbide
Pet roleum Processing, Chemicals and Addit ives, 1969.
48
Verst eeg, G.F., J. A. M. Kuipers, F.P.H. Van Beckum and W.P.M. Van Swaaij ,
"Mass Transfer wit h Complex Reversible Chemical React ions - I . Single
Reversible Chemical React ion", Chem. Eng. Sci., 44, 2295- 2310, 1989.
49
Winkelman, J.G.M., S.J. Brodsky and A.A.C.M. Beenackers, "Effect s of
Unequal Diffusivit ies on Enhancement Fact ors of Reversible React ions:
Numerical Solut ions and Comparison wit h Decoursey' s Met hod", Chem.
Eng. Sci., 47, 485- 489, 1992.
50
Zhang, Dan D., Gordon X. Zhao, H.-J. Ng, Y.- G. Li and X.- C. Zhao, An
Elect rolyt e Model for Amine Based Gas Sweet ening Process Simulat ion,
Preceeding of t he 78t h GPA Annual Convent ion, p25, 1999.
51
Zhange, Dan D., H.-J. Ng and Ray Vledman, Modeling of Acid Gas Treat ing
Using AGR Physical Solvent , Proceeding of t he 78t h GPA Annual
Convent ion, p62, 1999.
C- 26 Ref er ences
C- 26
Gl ycol Pr oper t y Pack age D- 1
D- 1
D Glycol Propert y Package
D.1 I nt r oduct i on ............. ........................................................... .......... 2
D.2 Pur e Component Vapor Pr essur e ......................................... .......... 3
D.3 Mi x i ng Rul es ............. ........................................................... .......... 4
D. 3. 1 TST Mixing Rules . ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 4
D. 3. 2 Zero- Pressure CEOS/ AE Mixing Rules. .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 6
D. 3. 3 Liquid GE Model . .. ... .. .. ... .. ... .. .. ... .. ... .. .. ... .. ... .. ... .. .. ... .. ... .. .. ... .. ... 8
D.4 Phase Equi l i br i um Pr edi ct i on ............................................... .......... 9
D.5 Ent hal py/ Ent r opy Cal cul at i ons ............................................ .........10
D.6 Ref er ences ............... ........................................................... .........10
D- 2 I nt r oduct i on
D- 2
D. 1 I nt roduct ion
I n t he gas processing indust ry, it is necessary t o dehydrat e/ remove
wat er vapour present in t he nat ural gas st ream. I n nat ure, impurit ies
like wat er vapor are mixed in t he nat ural gas.
Wat er vapor in t he gas st ream can cause t he following problems:
Hydrat e format ion, at low t emperat ure condit ions, t hat can plug
valves and fit t ings in gas pipelines.
React wit h hydrogen sulfide or carbon dioxide t o form weak
acids t hat can corrode gas pipelines.
The st andard met hod t o remove wat er vapor from nat ural gas st ream is
t o use t riet hylene glycol ( TEG) t o absorb t he wat er.
UniSim Design provides t he Glycol propert y package for use in
modeling glycol dehydrat ion process using TEG. This pr opert y package
is based on t he TST ( Twu- Sim-Tassone) equat ion of st at e. The propert y
package cont ains t he necessary pure component and binary int eract ion
paramet ers for component s commonly encount ered in nat ural gas
dehydrat ion process. The propert y package is t uned t o represent
accurat ely, t he phase behaviour of t hese component s, especially t hat
for t he TEG- wat er binary syst em.
The TST equat ion of st at e can accurat ely predict :
act ivit y coefficient s of t he TEG- wat er solut ions wit hin t he
average absolut e deviat ion of 2%
dew point t emperat ures wit hin an average error of
wat er cont ent of gas wit hin t he average absolut e deviat ion of
1%
The Glycol propert y package should be applicable over t he range of
t emperat ures, pressures, and component concent rat ion encount ered in
a t ypical TEG- wat er dehydrat ion syst em: bet ween 15C t o 50C and
bet ween 10 at m t o 100 at m for t he gas dehydrat or, and bet ween 202C
t o 206C and 1. 2 at mospheres for t he glycol regenerat or.
The t able below displays t he predict ion of equilibrium wat er cont ent in
lb
H2O
/ MMSCF for a gas st ream in cont act wit h 99. 5 weight percent TEG,
The accur acy of pr edi ct ed sol ubi l i t y of hydr ocar bons i n
aqueous phase i s ex pect ed t o be w i t hi n t he ex per i ment al
uncer t ai nt y.
Gl y col Pr oper t y Pack age D- 3
D- 3
using t he Glycol pr opert y package.
The figure below displays t he pr edict ed equilibrium wat er dew point vs.
cont act t emperat ur e at various TEG concent rat ions in weight %.
The BI P dat abank for t he Glycol propert y package will be updat ed in
fut ure releases of UniSim Design. Current ly, t here may be some
limit at ions or missing BI P for cert ain component pairs. For example,
heavy hydrocarbons or hypot het ical component s which may not have
any int eract ion paramet ers available. For assit ance in using t his
propert y package, please cont act Honeywell.
D. 2 Pure Component Vapor
Pressure
For t he Glycol propert y package, t hree alpha funct ion paramet ers are
used t o correlat e t he vapor pressure of t he component in t he UniSim
Design component dat abase. The alpha funct ion paramet ers are:
T dew ( K)
Repor t ed by : Pr edi ct ed f r om TST ( EOS) :
McKet t a
2
Buk acek
1
Wat er Cont ent Pr essur e ( Pa)
277. 59 390 396 393 838
266. 48 170 176 174 370
255. 37 70 72 71 151
244. 26 28 27 26 56.1
233. 15 9.2 9.1 9 18.7
222. 04 2.4 2.8 2.6 6
Fi gur e D. 1
D- 4 Mi x i ng Rul es
D- 4
L in Equat i on ( D. 6)
M in Equat i on ( D. 6)
N in Equat i on ( D. 6)
D. 3 Mixing Rules
For Glycol propert y package, t hree adj ust able paramet ers are used t o
correlat e Vapor- Liquid- Equilibrium ( VLE) mixt ure dat a. The paramet ers
corresponding t o t he TST ( Twu- Sim-Tassone) A
E
mixing rules are:
binary int eract ion paramet ers in Equat i ons ( D. 22) and
( D.23) .
D. 3. 1 TST Mixing Rules
The TST ( Twu et al. 2002
5
) cubic equat ions of st at e is:
where:
a, b = paramet ers values t hat correspond t o t he crit ical t emperat ure
of t he component
The crit ical t emperat ure ar e found by set t ing t he first and second
derivat ives of pr essure wit h r espect t o volume t o zero at t he crit ical
point :
where:
c = indicat es t he variable at t he crit ical point
The paramet er a is a funct ion of t emperat ure. The value of a( T) at
t emperat ures ot her t han t he crit ical t emperat ure is calculat ed using t he
( D. 1)
( D. 2)
( D. 3)
( D. 4)
A
ij
A
ji
o
ij
, , ,
P
RT
v b
--------
a
v 3b + ( ) v 0.5b ( )
--------------------------------- =
a
c
0.470507R
2
T
c
2
P
c
---- =
b
c
0.0740740R
T
c
P
c
---- =
Z
c
0.296296 =
D- 5
following equat ion:
where:
= funct ion of t he reduced t emperat ure
For vapor pr essure predict ion, t he Twu correlat ion ( Twu et
al., 1991
3
) is used:
For non- library component s, t he generalized alpha funct ion,
, is expressed as a funct ion of t wo variables: t he reduced
t emperat ure and t he acent ric fact or.
For non- library and pet roleum fract ions, t he generalized alpha
funct ion, , is:
Each is a funct ion of t he reduced t emperat ure only.
where:
L, M, N = dat abank values corresponding t o subcrit ical and
supercrit ical condit ions
( D. 5)
where:
L,M, N = paramet ers t hat are unique for each component
( D. 6)
( D. 7)
where:
= corresponds t o
= corresponds t o
( D. 8)
( D. 9)
(D.10)
a T ( ) o T ( )a
c
=
o T ( ) T
r
T T
c
=
o T ( )
o T ( ) T
r
N M 1 ( )
e
L 1 T
r
NM
( )
=
o T ( )
o o T
r
e , ( ) =
o T ( )
o o
0 ( )
e o
1 ( )
o
0 ( )
( ) + =
o
0 ( )
e 0 =
o
1 ( )
e 1 =
o
o
0 ( )
T
r
N
0 ( )
M
0 ( )
1 ( )
e
L 1 T
r
NM
0 ( )
\ .
| |
=
o
1 ( )
T
r
N
1 ( )
M
1 ( )
1 ( )
e
L 1 T
r
NM
1 ( )
\ .
| |
=
D- 6
D. 3. 2 Zero- Pressure CEOS/ A
E

Mixing Rules
The zero- pressure mixing rules for t he cubic equat ion of st at e mixt ur e a
and b paramet ers are as given:
The paramet ers and are defined as:
I n Equat i on ( D. 11)
= equat ion of st at e a and b paramet ers which are evaluat ed from
Par amet er s i n TST equat i on
T
r
1
T
r
> 1
L 0.196545 0.704001 0.358826 0.0206444
M 0.906437 0.790407 4.23478 1.22942
N 1.26251 2.13086 -0.20000 -8.00000
o
0
o
1
o
0
o
1
o
(D.11)
(D.12)
(D.13)
(D.14)
(
|
|
.
|
\
|
|
.
|
\
|
+ =
b
b
RT
A
RT
A
C b
a
b a
vdw
E
vdw
E
r vdw
vdw
ln
1
0 0
*
*
* *
* *
vdw
b b =
*
a
*
b
2 2
*
T R
Pa
a =
RT
Pb
b =
*
a
vdw
b
vdw
,
D- 7
t he van der Waals mixing rules
C
r
= function of reduced liquid volume r at zero pressure
u, w = equation of state dependent constants used to represent a
general two-parameter cubic equation of state
The reduced liquid volume r is assumed t o be a const ant ( r = 1. 18) ,
and C
r
is subsequent ly calculat ed as - 0. 5188496 in UniSim Design.
= excess Helmholtz energies of van der Waals fulid at zero pressure
Which can be approximat ed by , t he t he excess Helmholt z energy
of van der Waals fluid at infinit e pressure:
(D.15)
(D.16)
(D.17)
, ( for TST equat ion of st at e) (D.18)
(D.19)
( )
=
i j
ij j i j i vdw
k a a x x a 1
( )
+ =
i j
j i j i vdw
b b x x b
2
1
|
.
|
\
|
+
+
=
u r
w r
u w
C
r
ln
1
3 = u 5 . 0 = w
E
vdw
A
0
E
vdw
A
= =

i i
i
i
vdw
vdw vdw
E
vdw
b
a
x
b
a
C
RT
A
RT
A
*
*
*
*
1
0
0
D- 8
where:
D. 3. 3 Liquid G
E
Model
A general mult i- component equat ion for a liquid act ivit y model is now
proposed for incorporat ion in t he zero- pressure mixing rules as:
Equat i on ( D. 21) is similar t o t he NRTL equat ion but not t he same. The
NRTL assumes are t he paramet ers of t he model, but t he excess
Gibbs energy model assumes are t he binary int eract ion
paramet ers. More import ant , any appr opr iat e t emperat ure- dependent
funct ion can be applied t o and . For example, t o obt ain t he NRTL
model, are calculat ed fr om t he NRTL paramet er s :
Equat i on ( D. 21) can recover t he convent ional van der Waals mixing
rules when t he following expr essions are used for :
The above t wo equat ions ar e expressed in t erms of t he cubic equat ion
(D.20)
(D.21)
(D.22)
(D.23)
(D.24)
(D.25)
constant
1
1
ln
1
1
= |
.
|
\
|
+
+
=
u
w
u w
C
G
E
RT
----- x
i
x
j
t
ji
G
ji
j
n
x
k
G
ki
k
n
------------------
i
n
=
A
ij
A
ji
o
ij
, ,
t
ij
G
ij
,
ij
t
ij
G
t
ij
G
ij
, A
ij
A
ji
o
ij
, ,
t
ji
A
ji
T
----- =
G
ji
o
ji
t
ji
( ) exp =
t
ij
G
ij
,
t
ji
1
2
-- o
ij
b
i
=
G
ji
b
j
b
i
--- =
D- 9
of st at e paramet ers, and t he binary int eract ion paramet er .
D. 4 Phase Equilibrium
Predict ion
The following equat ions are t he TST ( Twu- Sim-Tassone) zero pressure
mixing rules used for phase equilibrium predict ion in t he Glycol
propert y package:
(D.26)
(D.27)

(D.28)
(D.29)
(D.30)
a
i
b
i
, k
ij
( )( ) b v b v
a
b v
RT
P
5 . 0 3 +
=
(
|
|
.
|
\
|
|
.
|
\
|
+ =
*
0 0
*
*
* *
ln
1
b
b
RT
A
RT
A
C b
a
b a
vdw
E
vdw
E
r vdw
vdw
* *
vdw
b b =
(
= =

i i
i
i
vdw
vdw vdw
E
vdw
b
a
x
b
a
C
RT
A
RT
A
*
*
*
*
1
0
0
=
n
i
n
k
ki k
n
j
ji ji j
i
E
G x
G x
x
RT
G
t
D- 10 Ent hal py/ Ent r opy Cal cul at i ons
D- 10
D. 5 Ent halpy/ Ent ropy
Calculat ions
The Glycol propert y package uses t he TST EOS for calculat ing ent halpy
and ent ropy of vapor phase, and t he Cavet t model for liquid/ aqueous
phase. Besides, t he Lee- Kesler met hod could also be chosen for
ent halpy and ent r opy calculat ion in Glycol propert y package.
D. 6 References
1
Bukacek, R.F., Equilibrium Moist ure Cont ent of Nat ural Gases, Research
Bullet in 8, I nst it ut e of Gas Technology, Chicago, I L, 1955.
2
McKet t a, J. J. and Wehe, A. H., cit ed by GPA Engineering Dat a Book, Fig. 15-
10, Nint h Edit ion, Fourt h Revision, Gas Processors Suppliers Associat ions,
Tulsa, OK, 1979.
3
Twu, C. H., Bluck, D., Cunningham, J.R., and Coon, J.E., A Cubic Equat ion of
St at e wit h a New Alpha Funct ion and a New Mixing Rule, Fluid Phase
Equilib. 1991, 69, 33- 50.
4
Twu, C.H., Tassone, V., Sim, D. W., and Wat anasiri, S., Advanced Equat ion of
St at e Met hod for Modeling TEG-Wat er for Glycol Gas Dehydrat ion, Fluid
Phase Equilibria, 2005 ( in press) .
5
Twu, C.H., Sim, W.D., and Tassone, V., A Versat ile Liquid Act ivit y Model for
SRK, PR, and A New Cubic Equat ion of St at e TST, Fluid Phase Equilibria,
2002, 194- 197, 385- 399.
I - 1
I ndex
A
Act ivit y Models 2- 9, A- 6, A- 20
See models - Chien Null, Margules, NRTL,
NRTL Opt ions, UNI QUAC, van Laar,
and Wilson
addit ional specificat ions 2- 17, 2- 95
binary int eract ion paramet ers 2- 52, 2- 100
choosing vapour phase model 2- 17, A- 22, A-
37
depart ure calculat ions A- 48
est imat ing int eract ion paramet ers 2- 53
immiscible liquid phases A- 24
Amines Propert y Package 2- 12, A- 44
Ant oine
modified vapour pressure model A- 41
paramet ers t ab 2- 43
vapour pressure model 2- 11, 2- 89
ASME St eam A- 46
propert y package 2- 12
Assay and Blend Associat ion 4- 69
Assay Dat a
general guidelines 4- 29
no dist illat ion dat a available 4- 26, 4- 29
physical propert ies 4- 22
st andard input 4- 26
Assays
charact erizing 4- 11, 4- 14
correlat ions 4- 44
input t ing 4- 16
light ends 4- 30
analysis B- 4
aut o calculat ing 4- 34, B- 6
included 4- 31
input t ing 4- 32
light ends free 4- 32
not es 4- 47
plot t ing 4- 43
select ing 4- 48
t ypes of 4- 42
user curves 4- 46
working curves 4- 42
ASTM D1160. See Laborat ory Assay Procedures
Aut o Cut 4- 51
B
Basis Environment 1- viii
Basis Manager
component maps t ab 6- 2
fluid package t ab 2- 2
hypot het icals t ab 3- 3
oil manager t ab 4- 8
react ions t ab 5- 2
user propert ies t ab 7- 3
Benedict - Webb- Rubin- St arling ( BWRS) 2- 8
Blends
aut o cut t ing 4- 51
bulk dat a 4- 49
composit e plot s 4- 59
correlat ions 4- 54
cut ranges 4- 50
dist ribut ion plot s 4- 57
informat ion 4- 55
not es 4- 60
oil dist ribut ions 4- 56
plot s summary 4- 60
propert y plot s 4- 56
Braun K10 2- 11, 2- 89, A- 43
Bubble Point A- 68
Bulk Propert ies 4- 22
BWR Equat ion A- 10
BWRS A- 15
C
Cavet t Correlat ion A- 48
CCO 2- 72
Chao Seader A- 5A- 6, A- 40
models 2- 10, 2- 89
semi- empirical met hod 2- 10, 2- 90
Chien Null A- 22, A- 24
act ivit y model 2- 9
paramet ers t ab 2- 41, 2- 96
Chromat ographic Analysis. See Laborat ory Assay
Procedures
Chromat ographic Assay I nput 4- 28
Coal Analysis 3- 30
Collect ion ( Component Maps) 6- 2
Component List Select ion 2- 12, 2- 93
Component Select ion 1- 12
family filt er 1- 11
family t ype filt er 1- 11
filt er opt ions 1- 11
general procedure 1- 8
propert y package filt er 1- 11
t ips 1- 8
warning messages 2- 13
Component s
adding 1- 5
cloning. See Hypot het icals, cloning library
component s
creat ing cust om. See Hypot het icals, adding
filt ering 1- 9
hypot het icals quick access 1- 29
incompat ible 2- 14
manager 1- 2, 8- 2, 9- 2
mapping 6- 2
mast er component list 1- 2
name format 1- 81- 9
Index I-2
I - 2
non recommended 2- 13
paramet ers t ab 2- 22, 2- 96
removing 1- 7, 1- 13
select ed component s group 1- 6
select ion 1- 8, 1- 12
sort ing 1- 7, 1- 14
subst it ut ing 1- 7, 1- 13
synonyms 1- 8
t ransferring 1- 12
viewing 1- 7, 1- 15
Component s Manager 1- 2
Conversion React ions 5- 65- 10
rank 5- 35
Correlat ions
assay 4- 44
blend 4- 54
crit ical propert y B- 8
oil charact erizat ion 4- 64
Cubic EOS
mixing rules D- 6
Cut 4- 50
Cut / Blend. See Blends or Oil Charact erzat ion
Cut point B- 6
D
D86 I nt erconversion Met hods 4- 12
D86. See Laborat ory Assay Procedures
Densit y. See Liquid Densit y or Vapour Densit y
Dew Point A- 67
E
EFV ( Equilibrium Flash Vapourizat ion) . See
Laborat ory Assay Procedures
Eley- Rideal Model 5- 22
Ent halpy Basis A- 46
t abular 2- 76
Ent halpy Depart ure Calculat ions A- 46
Ent halpy Flash A- 68
Ent ropy Flash A- 68
Equat ions of St at e ( EOS) 2- 8, A- 8
addit ional informat ion 2- 15, 2- 95
depart ure calculat ion A- 46
int eract ion paramet ers 2- 49, 2- 98
See models - Generalized Cubic ( GCEOS) ,
Kabadi Danner, Lee- Kesler Plocker,
Peng Robinson, PRSV, Peng Robinson
Opt ions, SRK, SRK Opt ions,
Zudkevit ch Joffee.
TST CEOS D- 4
Equat ions of St at e Ent halpy Calculat ion A- 19
Equilibrium React ions 5- 6, 5- 105- 16
fract ional approach 5- 15
t emperat ure approach 5- 15
Esso Tabular A- 43
vapour pressure model 2- 11, 2- 89
Ext ended NRTL. See NRTL Opt ions
F
Flash Calculat ions A- 65
handling wat er A- 70
t emperat ure- pressure ( TP) A- 66
vapour fract ion A- 67
Flow Rat e
act ual gas A- 64
act ual volume A- 64
as a specificat ion A- 65
available A- 60
densit ies, liquid and vapour A- 61
liquid volume A- 63
mass A- 63
molar A- 63
st andard gas A- 64
st andard liquid volume A- 64
volumet ric A- 60
Fluid Package
act ivit y models 2- 9
adding 2- 3
adding - quick st art 2- 4
adding not es 2- 83
advant ages 2- 2
associat ed flowsheet 2- 3
base propert y select ion 2- 7
copy 2- 3
delet e 2- 3
equat ions of st at e 2- 8
export 2- 3
import 2- 3
propert y package select ion 2- 7
propert y view 2- 6, 2- 84
react ions 2- 62
st abilit y t est 2- 56, 2- 102
t abular 2- 63
See also Tabular Package
Fugacit y Coefficient s A- 51
G
General NRTL. See NRTL Opt ions
Generalized Cubic Equat ion of St at e ( GCEOS) 2- 8
binary coeffs t ab 2- 44
Glycol
Glycol Propert y Package D- 2
ent halpy calculat ion D- 10
ent ropy calculat ion D- 10
liquid act ivit y model D- 8
mixing rules D- 4
phase equilibrium predict ion D- 9
pure component vapor pressure D- 3
Grayson St reed A- 5A- 6, A- 40
Index I-3
I - 3
semi- empirical met hod 2- 10, 2- 90
H
Henry' s Law A- 35
Het erogeneous Cat alyt ic React ions 5- 6, 5- 215-
26
Eley- Rideal 5- 22
Langmuir- Hinshelwood 5- 22
Mars- van Krevelen Model 5- 22
Hypot het ical Component s. See Hypot het icals
Hypot het ical Group
cont rols 3- 12
creat ing 3- 4, 3- 11
delet ing 3- 4
export ing 3- 4
group name 3- 12
import ing 3- 4
moving 3- 35
moving bet ween 3- 5
viewing 3- 4, 3- 35
Hypot het icals
adding 1- 29, 3- 13
adding a hypot het ical - quick st art 3- 5
adding hypot het ical group 1- 30
base propert ies 3- 13
cloning library component s 3- 5, 3- 12, 3- 33
crit ical propert ies 3- 23
delet ing 3- 13
est imat ing propert ies 3- 12, 3- 23
est imat ion met hods 3- 12, 3- 15
individual cont rols 3- 12
minimum informat ion required 3- 15
moving 3- 5
propert y view 3- 21
quick reference 3- 4
solid hypot het icals 3- 13, 3- 28
t emperat ure dependent propert ies 3- 26
UNI FAC st ruct ure builder 3- 13, 3- 19
vapour pressure propert ies 3- 14
viewing 3- 5, 3- 13
viewing group. See Hypot het ical Group,
viewing
I
I deal Gas Law A- 38
I nst alling
oils 4- 11
react ion set 5- 37
I nt eract ion Paramet ers
act ivit y models 2- 52, 2- 100, A- 22
equat ions of st at e 2- 49, 2- 98
est imat ing A- 20
Henrys Law A- 36
K
K/ ln( K) Equilibrium Const ant 5- 14
Kabadi Danner A- 8, A- 10
equat ion of st at e 2- 8
Kinet ic React ions 5- 165- 21
requirement s 5- 6
L
Laborat ory Assay Procedures
ASTM D1160 4- 5, 4- 25
ASTM D2887 4- 5, 4- 26
ASTM D86 4- 5, 4- 25
ASTM D86 and D1160 4- 26
chromat ographic analysis 4- 6, 4- 26
assay input 4- 28
D2887 int erconversion met hod 4- 13
D86 int erconversion met hod 4- 12
equilibrium flash vapourizat ion 4- 5, 4- 26
preparat ion 4- 31
TBP analysis 4- 5, 4- 25
Langmuir- Hinshelwood Model 5- 22
Lee Kesler Plocker 2- 8, A- 8, A- 10
Lee- Kesler Ent halpy A- 19, A- 40, A- 50
Liquid Densit y A- 53
act ual A- 62
ideal A- 62
st andard A- 62
M
Mapping
collect ion 6- 2
component s 6- 1
t arget 6- 2
t ransfer opt ions 6- 4
Margules A- 22, A- 29
Mars- van Krevelen Model 5- 22
MBWR A- 14
N
NBS St eam A- 46
NRTL ( Non Random Two Liquid) A- 21, A- 24, A- 30
NRTL Opt ions A- 24
Ext ended NRTL 2- 9, A- 27
General NRTL 2- 10, A- 27
O
analysis met hods. See Laborat ory Assay
Procedures
Index I-4
I - 4
bulk blending dat a 4- 49
component crit ical propert ies B- 8
composit e plot s 4- 59
correlat ions 4- 7, 4- 11, 4- 44, 4- 64
cut t ing/ blending 4- 11, 4- 47
delet ing 4- 11
densit y curves 4- 38
det ermining TBP cut point s B- 6
dist ribut ion plot s 4- 57
FBP 4- 12
I BP 4- 12
inst alling oil 4- 69
laborat ory dat a correct ions 4- 7
light ends 4- 304- 32, B- 4
met hod B- 2
molecular weight curves 4- 37
not es 4- 69
out put set t ings 4- 12
physical propert y curves 4- 7, 4- 28
procedure 4- 8
propert y plot s 4- 56
propert y view 4- 11
purpose 4- 3
user propert ies 4- 11, 4- 61
viscosit y curves 4- 38
working curves 4- 42
P
Peng Robinson A- 4A- 5, A- 8
fugacit y coefficient A- 52
modelling vapour phase A- 38
Peng Robinson Opt ions A- 8
PRSV 2- 9
Sour PR 2- 9, A- 13
Physical Propert ies A- 52
Poynt ing Correct ion 2- 18, A- 22
PPDS 2- 722- 73
Propert y Package
select ing a A- 4
Propert y Packages
See Amines Propert y Package, Braun K10,
Chao Seader, Esso Tabular, Grayson
St reed, Lee Kesler Plocker, Margules,
MBWR, PRSV, Peng Robinson,
Peng Robinson Opt ions, SRK, SRK Opt ions,
St eam Packages, UNI QUAC, van Laar
and Wilson.
PRSV ( Peng Robinson St ryj ek Vera) A- 5, A- 11
PR- Twu, SRK- Twu, Twu- Sim- Tassone ( TST) A- 17
Pseudo Component Generat ion 4- 47
PVT Environment 8- 2, 9- 2
Q
Qualit y Pressure A- 68
R
React ion Package
adding 5- 38
React ion Rank 5- 35
React ion Set s 5- 29
adding 5- 30
adding t o fluid package 5- 30, 5- 37
advanced feat ures 5- 32
at t aching t o unit operat ions 5- 37
copying 5- 30
delet ing 5- 30
export ing 5- 30, 5- 36
import ing 5- 30, 5- 36
quick access 2- 63
solver met hod 5- 31
viewing 5- 30
React ions
act ivat ing 5- 31
adding 5- 7
component s 5- 3
conversion. See Conversion React ions
copying 5- 7
deact ivat ing 5- 32
delet ing 5- 7
equilibrium. See Equilibrium React ions
het erogeneous cat alyt ic. See Het erogeneous
Cat alyt ic React ions
kinet ic. See Kinet ic React ions
library react ions 5- 5
quick st art 5- 39
select ing component s 5- 2, 5- 4
set s. See React ion Set s
simple rat e. See Simple Rat e React ions
t hermodynamic consist ency 5- 18
viewing 5- 7
Redlich Kwong ( RK) A- 38
S
Simple Rat e React ions 5- 265- 29
requirement s 5- 6
Solids A- 72
Sour PR. See Peng Robinson Opt ions
Sour SRK. See SRK Opt ions
Sour Wat er Opt ions A- 13
See SRK Opt ions and Peng Robinson Opt ions
SRK ( Soave Redlich Kwong) A- 5A- 6, A- 8
fugacit y coefficient A- 52
SRK Opt ions A- 8
Index I-5
I - 5
See Kabadi Danner and Zudkevit ch Joffee
Sour SRK 2- 9, A- 13
St abilit y Test 2- 54, 2- 100
paramet ers 2- 56, 2- 102
St eam Packages A- 45
See ASME St eam and NBS St eam
St ream I nformat ion A- 73
Surface Tension A- 59
T
Tabular Package 2- 63
act ive propert ies select ion 2- 69
dat a 2- 71
ent halpy basis 2- 76
library 2- 722- 73
plot t ing 2- 73
regression 2- 77
requirement s 2- 65
supplying dat a 2- 76
using 2- 66
viewing select ion 2- 73
Target ( Component Maps) 6- 2
TEG D- 2
Thermal Conduct ivit y A- 56
Transport Propert ies A- 52
Triet hylene glycol D- 2
TST
mixing rules D- 4
U
UNI FAC LLE
int eract ion paramet er est imat ion 2- 53
UNI FAC Propert y Est imat ion A- 23
UNI FAC St ruct ure Builder 3- 19
UNI FAC VLE
int eract ion paramet er est imat ion 2- 53
UNI QUAC ( Universal Quasi Chemical Paramet ers)
2- 10, A- 21, A- 31
User Point s 4- 51
User Propert ies 4- 46, 4- 61, 7- 27- 8
adding 7- 3
delet ing 7- 3
mixing rules 7- 6
not es 7- 8
viewing 7- 3
User Ranges 4- 52
V
van Laar A- 22, A- 33
Vapour Densit y A- 53
Vapour Pressure A- 68
Vapour Pressure Models 2- 11, A- 6, A- 41
Ant oine 2- 11, 2- 89
Braun K10 2- 11, 2- 89
Esso Tabular 2- 11, 2- 89
Virial Equat ion A- 22
Viscosit y A- 54
liquid phase mixing rules A- 55
W
Wat er A- 70
Wilson 2- 10, A- 21, A- 34
Working Curves B- 3
Z
Zudkevit ch Joffee A- 8, A- 13
Index I-6
I - 6

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Uni Si m Desi gn

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A- 30 Pr oper t y Met hods

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