Process Simulation V 2016

Unit 3-5-1
Process Simulation V
Reactor Design and
Performance
Copyright, The University Of Adelaide, Australia.
3030/7054 Reactor
3-5-1
Unit 3-5-2
Reactor Performance
Production of Desired Product

Conversion
Yield
Selectivity
Reactor
Performance
Chemical Reactor
Volume
Residence Time
Catalyst
Reactor model
Reactor Configuration
Reaction Kinetics
Concentration
Temperature
Pressure
Reaction Mechanism
Catalyst
Thermodynamic Limitations
Heat Transfer
Exothermic
Endothermic
Heat Exchange Configuration
3030/7054 Reactor
3-5-2
Unit 3-5-3
Chemical Reactions
Chemical Reactions
Single reactions A+B C

Parallel reactions A+B C BD
Series reactions A+B CE
Series and parallel reactions A+B CE BD
Reaction
Conversion
Yield
Selectivity
Reaction kinetics and thermodynamics

Thermodynamics sets limits on possible conversion in a
reacting system
Chemical reactors
CSTR, PFR, Fluidized Reactor, Moving Bed Reactor, etc.
3030/7054 Reactor
3-5-3
Reactor Simulation and Design
Unit 3-5-4
What is the product composition for given feed

composition & process conditions?
What is the heat of reaction at process temperature and
pressure?
How much catalyst is needed to achieve the desired
conversion
What is the rate of catalyst make-up or regeneration?
What other feed or process conditions must be
controlled?
What is the reactor size to achieve the desired
conversion?
3030/7054 Reactor
3-5-4
Level I Input for Reactors
Unit 3-5-5
b
c
d
A+ B C+ D
a
a
a
r = k pA1.5 pB0.5
k=A e(-Ea/RT)
Unit of r; k; A
Forward order
Base component
Reaction phase
3030/7054 Reactor
3-5-5
Unit 3-5-6
Reactions in Hysys
Conversion
Reaction equations
No need of any thermodynamic knowledge
Conversion rate (C=Co+C1*T+C2*T2) (C must be less than 100)
Can not be grouped with other types of reactions in the reaction set
Can be grouped with other conversion reactions and ranked to
operate simultaneously or sequentially
Lowest ranking occurs first
Can not be used with PFR or CSTR.
can not provide sizing information
Input thermal mode of operation
Only basic M&E balances are performed
Can be useful for the first-time simulation of a process
3030/7054 Reactor
3-5-6
Unit 3-5-7
Conversion
b
c
d
A+ B C + D
a
a
a
N A = N A0 (1 X A )
b
N B = N B 0 N A0 X A
a
c
N C = N C 0 + N A0 X A
a
d
N D = N D 0 + N A0 X A
a
a, b, c, d the respective
stoichiometric coefficient of the
reacants (A& B) and products (C&
D)
A==the base reactant
B=the base reactant not in the
limiting quantity
N*--the final moles of components
A to D
N*0-the initial moles of
components A to D
XA the conversion of the base
component A
In HYSYS, C must be between 0-100

3030/7054 Reactor
3-5-7
Unit 3-5-8
Reactions in Hysys
Equilibrium
aA + bB cC + dD
Reaction equations
[C ]c [ D]d
Specify Keq by
K=
a
b
[
A
]
[
B
]
A constant: Ln(Keq) or Keq;
Gibbs free energy;
ln Keq = G(reaction) / RT
o
Valid at T=25-426.85 C
Ideal Gas Gibbs Free Energy Coefficients
Gibbs reaction takes non ideal into consideration
A function of T;
A,B,C,D,E,F,G,H :constants ln( Keq ) = a + b
T unit: Kelvin
B
Keq vs T table.
a = A + + CLn (T ) + DT
T
Only used with equilibrium or
general reactors
b = ET 2 + FT 3 + GT 4 + HT 5
3030/7054 Reactor
3-5-8
Unit 3-5-9
Reactions in Hysys
Gibbs
No reaction set
Minimizing the total Gibbs free energy of the effluent mixture
To provide the theoretical conversion limits
Kinetic Reactor (PFR or CSTR)

Reaction set
Reactor type
Kinetics rate constant
Kinetic
Heterogeneous Catalytic Reaction
Simple rate reaction
Sizing reactor available !
3030/7054 Reactor
3-5-9
Unit 3-5-10
Kinetic Reaction
aA + bB cC + dD
rA = kf (Basis) k ' f (Basis)
k = forward reaction rate

constant
k' = reverse reaction rate
constant
A, E, , Arrhenius Parameters
for the forward reaction.
A', E', Arrhenius Parameters
for the reverse reaction.
dN A
FA0 FA + VrA dV =
dt
$ E '
k = A exp &
)T
% RT (
Example : CO + Cl2 COCl2
$ E' '
k ' = A'exp &
)T '
rCO = k[CO][Cl2 ]
% RT (
1
k
rHysys = r c
for catalyst-based PFR
K eq =
k'
3/2
3030/7054 Reactor
3-5-10
Heterogeneous Catalytic Reaction

Unit 3-5-11
aA + bB cP
(kinetic term)(potential term)
r =
(adsorption term)
k + K A K B C AC B
r=
(Langmuir - Hinshelwood model)
2
(1 + K AC A + K B C B + K P C P )
k + K B C AC B
r=
(Eley - Rideal Model)
(1 + K B C B + K P C P )
kC A
r=
(Mars - van Krevelen Model)
n
*
1 + (a / b)(k / k )CAC B
3030/7054 Reactor
3-5-11
HCR
Unit 3-5-12
k* = the adsorption rate constant for component *

k+ = the forward reaction rate constant
k = reaction rate constant for oxidation of hydrocarbon
k* = reaction rate constant for surface re-oxidation
In Hysys, generalised form:
reac tan ts
kf
r=
Ci i k r
i =1
Pr oducts
Cj
j =1
g
1 + K k C g
k =1 g =1
kf,kr = rate constant of the

forward and reverse kinetic
rate expressions
K= the adsorption rate
constant
M-number of adsorbed
reactants and products plus
inert species
3030/7054 Reactor
3-5-12
Unit 3-5-13
Simple Rate Reaction
aA + bB cC + dD
rA = kf ( Basis) k ' f ( Basis / K eq )
dN A
FA0 FA + VrA dV =
dt
E
k = A exp
T
RT
ln( K eq ) = A'+ B ' / T + c' Ln (T ) + D ' T
T must be in Kelvin Unit !
3030/7054 Reactor
3-5-13
Unit 3-5-14
Example 3-5-1
Considering the following reaction starting with

natural gas feed. Reactions are
CH 4 + H 2O 3H 2 + CO (1)
CO + H 2O H 2 + CO 2
(2)
Reaction (1) is the reforming reaction and reaction (2)

is water gas shift reaction, an equilibrium reaction.
Reaction (1) can be modelled by LangmuirHinshelwood equation
E
a1
DBED * k m * e RT * P * ym
r1 =
1 + K h * P * yh
Reaction (2) uses the Estandard kinetic form
r2 = DBED * A * e
a2
RT
* ( yc * yw yd * yh / K eq 2 )
3030/7054 Reactor
3-5-14
Unit 3-5-15
Example cont.
Variable
Abbreviation
Value
Units
Bed Density
DBED
1200
kg/m3
Pre-exponential Rate Constant
km
5.517e6
mol/kg/s/atm
Activation Energy of Reaction 1
Ea1
1.849e8
J/mol
Gas Constant
8.314
J/mol/K
Pressure
30.0
atm
Absorption Parameter
Kh
4.053
atm-1
Mole fraction of CH4
ym
Varies
Unitless
Mole fraction of CO
yc
Varies
Unitless
Mole fraction of H2
yh
Varies
Unitless
Mole fraction of H2O
yh
Varies
Unitless
Pre-exponential Rate Constant
4.95e8
mol/kg/s
Activation Energy of Reaction 2
Ea2
1.163e5
J/mol
Equilibrium Constant1
Keq2
e-4.946 + 4897/T
Unitless (T in K)
3030/7054 Reactor
3-5-15
Unit 3-5-16
Example-Cont.
1 Correctly set up all parameters for

kinetic equations
2 Compare the performance of the
kinetic reactors with Gibbs and
Equilibrium Reactors.
3030/7054 Reactor
3-5-16
Unit 3-5-17
Example Cont.
3030/7054 Reactor
3-5-17
Reactor Set-up
Unit 3-5-18
Reaction (1) has a format of Langmuir-Hinshelwood

equationchoosing the heterogeneous catalytic reaction
Comparing Hysys general format and r1 given from the
reaction information
reac tan ts
kf
r=
Ci k r
i =1
Pr oducts
j =1
g
1 + K k C g
k =1 g =1
Ea1
RT
DBED * k m * e
* P * ym
r1 =
1 + K h * P * yh
k f = DBED * k m * e
Ea1
RT
= A*e
Ea 1
RT
In the numerator: No reversion reaction; in the forward

reaction, only methane, based on partial pressure
In the denominator, only hydrogen, n=1
3030/7054 Reactor
3-5-18
Unit 3-5-19
Setup cont.
The reaction basis is partial pressure with a unit of atm,

and the reaction in the vapour phase.
3030/7054 Reactor
3-5-19
Unit 3-5-20
Setup cont.
Only methane has a forward order of 1.0; others are set

as 0.0
A=DBED*km =1200 kg/m3* 5.517e6 mol/kg/s/atm
=6.6204E9 mol/(m3 s atm) = 6.6204E6 kmol/(m3 s atm)
E=1.849E8 J/mol =1.849E8 KJ/kmol
3030/7054 Reactor
3-5-20
Unit 3-5-21
Setup cont.
A=Kh = 4.053 atm-1, only hydrogen is chosen for this

case in the denominator.
n=1
3030/7054 Reactor
3-5-21
Setup cont.
Unit 3-5-22
Reaction (2) is a kinetic reaction with an equilibrium

constant, so this reaction is modelled by simple rate
reaction
rA = kf ( Basis) k ' f ( Basis / K eq )
E
k = A exp
T
RT
ln( K eq ) = A'+ B' / T + c' Ln (T ) + D' T
K eq 2 = -4.946 + 4897/T
r2 = DBED * A * e
Ea 2
RT
* ( yc * yw yd * yh / K eq 2 )
Reaction basis is molar fraction; A=DBED*A; E=Ea2;

A=-4.946; B=4897; =0;
3030/7054 Reactor
3-5-22
Unit 3-5-23
Setup cont.
A=1200 kg/m3* 4.95e8 mol/kg/s =5.94E11 mol/m3s

= 5.94E8 kmol/m3s
E=Ea2= 1.163e5 J/mol = 1.163E5 kJ/kmol =2.8E5 kcal/
kmol
A=-4.946; B=4897;
3030/7054 Reactor
3-5-23
Unit 3-5-24
Results from Kinetics
Kinetic reaction set includes the above two reactions,

attached to Antoine package
Set the reactor size as 10 m in length and 2.21 in
diameter; void fraction as 1.0
3030/7054 Reactor
3-5-24
Unit 3-5-25
Reactor Comparison
Using the same feed, choosing Gibbs reaction without

any reaction set
Using the same feed, choosing equilibrium reactor with
the Keq vs T with a table
The results are compared
Reforming reaction has a low reaction rate in the kinetic
model.
Methane molar flow increasing from both Gibbs and
Equilibrium comparing with kinetic reactions
Both Gibbs and Equilibrium have quite similar results.
Changing equilibrium constant to calculate from Gibbs free
energy, the results are even closer
Only choosing the water gas shift reaction of the reaction set in
the Equilibrium reactor, very similar results as kinetic reactor
can be obtained
3030/7054 Reactor
3-5-25
Unit 3-5-26
Comparison Cont.
3030/7054 Reactor
3-5-26
Level II with Heat Transfer
Unit 3-5-27
Reactor equations
Energy balance on reaction side
Energy balance on heat transfer
medium side
Heat transfer performance equation
(Q=UATm)
Pressure drop in packed bed (Ergun
Equation)
3030/7054 Reactor
3-5-27
Heat Transfer in Reactors
Unit 3-5-28
3030/7054 Reactor
3-5-28
Unit 3-5-29
3030/7054 Reactor
3-5-29
Unit 3-5-30
Reactor Sizing Steps
Using Gibbs reactor to determine the theoretical

conversion limit
Residence time and volumetric flow rate are used to
size reactors
Using Adjust Function to determine the reactor
volume
Check the conversion at the calculated dimensions
less than the conversion limit.
3030/7054 Reactor
3-5-30
Unit 3-5-31
Heuristics for Reactors
Dimensions of catalyst particles are 0.1 mm in

fluidized beds, 1 mm in slurry beds, and 2-5 mm in
fixed beds.
The optimum proportions of stirred tank reactors are
with liquid level equal to the tank diameter
Tubular flow reactors are suited to high production
rates at short residence times (sec or min) and when
substantial heat transfer is needed
PFR contains 20 segments in Hysys. Each segment
represents ideal CSTR.
3030/7054 Reactor
3-5-31
Unit 3-5-32
Numerical Methods
Newton's Method.
usually converges quickly
Default method
Rate Iterated.
A partial Newton's method, and assumes that the offdiagonal elements of the Jacobian matrix are equal to zero.
The Method works well when there is very little interaction
between reactions.
Rate Integrated.
This method integrates the reaction equations until all time
derivatives are zero.
stable, but slow.
3030/7054 Reactor
3-5-32
Unit 3-5-33
Tips and Hints
After creating the reaction, need to create a reaction

set and attach the reaction set to a fluid package.
Always check the unit for the reaction kinetic data A
and E
Always choose the reaction phase
3030/7054 Reactor
3-5-33
Unit 3-5-34
Example 3-5-2
You are working as a process engineer to design an acetone

production unit. One of key parameter is the number of tubes. You are
asked to calculate the process using Hysys. Basic information:
Acetone is produced by endothermal reaction
(CH3)2CHOH (isopropyl alcohol)(CH3)2CO (acetone) + H2
No significant side reactions. The reaction takes place in the gas phase
on a solid catalyst with a kinetics rIPA = k cIPA kmol/m3 reactor s
Where k = 3.156x105 exp(-8720/T) where T is in K.
The current process uses a PFR with a heat transfer medium, HTM, on
the shell side, at 1x105 kgmol/hr and the heat capacity is 75 KJ/Kmol/C
Because there is a concern about operation of the downstream
separation section, the IPA reaction conversion is held constant at 90%
to ensure a constant feed composition to the separation section even
though the flow rate of this stream may change.
3030/7054 Reactor
3-5-34
Unit 3-5-35
Flowrate (kmol/h)
234
stream
2.16
feed
feed
acetone
0.16
IPA
38.64
water
19.04
Equipment
Specifications
Reactor
MOC: carbon steel
Tube
Number-??
Diameter 2 in
Length 20 ft
Wall Heat transfer
coefficient
60 W/(m2 oC)
hydrogen
oC
bar
350
350
1.91
htm in
htm out
reactor
effluent
3030/7054 Reactor
3-5-35
Reactor Setup
Unit 3-5-36
234
2.16
Flowrate (kmol/h)
stream
feed
hydrogen
acetone
0.16
IPA
38.64
water
19.04
3030/7054 Reactor
3-5-36
Unit 3-5-37
Heat Transfer
dP:
Ergun
Eqn
Duty
param
eters:
Formu
la
Input
Hysys
Default
3030/7054 Reactor
3-5-37
Unit 3-5-38
Reactor Rating
Diameter
Height
Leave number of tubes empty
Wall thickness 5.00E-03 m as default
Void fraction 0.9
Adjust function to adjust the conversion
rate as a function of reactor volume.
3030/7054 Reactor
3-5-38
ResultsMaterial Stream
Unit 3-5-39
3030/7054 Reactor
3-5-39
Unit 3-5-40
Results - Reactor
3030/7054 Reactor
3-5-40
Unit 3-5-41
Option 1 No Formula
Use Direct Q Value Option, and set the outlet temperature of

Stream 2 as 350 C. The results are below. The utility fluid is
from Hysys Default.
Use Formula, the exit temperature is 344.8 C, and number of

tubes is 307 !
3030/7054 Reactor
3-5-41
Unit 3-5-42
Summary
Hysys reactor setups for kinetics,

conversion, equilibrium and Gibbs
reactors
Reactors with heat-transfer
Reactor sizing
3030/7054 Reactor
3-5-42
Unit 3-5-43
References
3030/7054 Reactor
3-5-43

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Unit 3-5-1

Copyright, The University Of Adelaide, Australia.

Production of Desired Product

Copyright, The University Of Adelaide, Australia.

Single reactions A+B C

Reaction kinetics and thermodynamics

Reactor Simulation and Design

What is the product composition for given feed

Copyright, The University Of Adelaide, Australia.

Level I Input for Reactors

Copyright, The University Of Adelaide, Australia.

Copyright, The University Of Adelaide, Australia.

In HYSYS, C must be between 0-100

Kinetic Reactor (PFR or CSTR)

Sizing reactor available !

Copyright, The University Of Adelaide, Australia.

k = forward reaction rate

Copyright, The University Of Adelaide, Australia.

Heterogeneous Catalytic Reaction

Copyright, The University Of Adelaide, Australia.

k* = the adsorption rate constant for component *

Copyright, The University Of Adelaide, Australia.

kf,kr = rate constant of the

Simple Rate Reaction

Copyright, The University Of Adelaide, Australia.

Considering the following reaction starting with

Reaction (1) is the reforming reaction and reaction (2)

Copyright, The University Of Adelaide, Australia.

Pre-exponential Rate Constant

Activation Energy of Reaction 1

Mole fraction of CH4

Mole fraction of H2O

Pre-exponential Rate Constant

Activation Energy of Reaction 2

Copyright, The University Of Adelaide, Australia.

1 Correctly set up all parameters for

Copyright, The University Of Adelaide, Australia.

Copyright, The University Of Adelaide, Australia.

Reaction (1) has a format of Langmuir-Hinshelwood

In the numerator: No reversion reaction; in the forward

Copyright, The University Of Adelaide, Australia.

The reaction basis is partial pressure with a unit of atm,

Copyright, The University Of Adelaide, Australia.

Only methane has a forward order of 1.0; others are set

Copyright, The University Of Adelaide, Australia.

A=Kh = 4.053 atm-1, only hydrogen is chosen for this

Copyright, The University Of Adelaide, Australia.

Reaction (2) is a kinetic reaction with an equilibrium

Reaction basis is molar fraction; A=DBED*A; E=Ea2;

A=1200 kg/m3* 4.95e8 mol/kg/s =5.94E11 mol/m3s

Copyright, The University Of Adelaide, Australia.

Results from Kinetics

Kinetic reaction set includes the above two reactions,

Copyright, The University Of Adelaide, Australia.

Using the same feed, choosing Gibbs reaction without

Copyright, The University Of Adelaide, Australia.

Level II with Heat Transfer

Copyright, The University Of Adelaide, Australia.

Heat Transfer in Reactors

Copyright, The University Of Adelaide, Australia.

Copyright, The University Of Adelaide, Australia.

Reactor Sizing Steps

Using Gibbs reactor to determine the theoretical