Example of HDA

AN EXAMINATION OF MODIFIED HIERARCHICAL DESIGN
STRUCTURE FOR CHEMICAL PROCESSES

by
STANISLAV VALERIEVICH EMETS, B.S.
A THESIS
IN
CHEMICAL ENGINEERING
Submitted to the Graduate Faculty
of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
MASTER OF SCIENCE
IN
CHEMICAL ENGINEERING
Approved
Chairper/on of the Committee
Accepted
Dean of the Graduate School
May. 2003
ACKNOWLEDGMENTS
1 am delighted to sa> that the outcome of this project vva.s very valuable and worth
the effort spent. 1 thank my father, mother, and sister whose love and affection enabled
me to accomplish this project.
1 would like to express m>- gratitude to Professor Uzi Mann, the chairman of my
thesis committee, for his guidance, support, and influence. Not only has he taught me a
lot technically, but also he was a true mentor. I also thank Professor Karlene Hoo for all
the knowledge and skills that I learned from her, for all the suggestions that she has given
me in completing my master's thesis successfully, and for serving on my committee.
1 also want to express my appreciation and thanks to the Phillips Petroleum
Company for providing the fellowship that enabled me to pursue graduate studies in
chemical engineering at Texas Tech Universitx.
I would like to thank all my peers at Texas Tech for their encouragement and
support during my work on the Master of Science degree.
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT v
LIST OF TABLES M,
LIST OF FIGURES ix
NOMENCLATURE xi
ABBREVIATIONS xu
CHAPTER
1 OBJECTIVES AND MOTIVATION 1
2 CONVENTIONAL HIERARCHICAL DESIGN STRUCTURE
AND HDA PROCESS 4
2.1 Background 4
2.2 Design Objectives and Process Specifications 6
2.3 Process Conditions and Constraints 7
2.4 Thermodynamic and Kinetic Data 8
2.5 The Conventional HDA Design 13
3 THE MODIFIED HDA PROCESS 17
4 ANALYSIS: COMPARISON OF THE MODIFIED AND THE
CONVENTIONAL DESIGNS 26
4.1 Economic Potential and Profit Rate 26
4.2 Capital Cost Investment 28
4.3 Performance Comparison
Ul
5 CONCLUSIONS AND RECOMMENDATIONS 37
BIBLIOGRAPHY 40
APPENDIX
A CALCULATION OF 11 lERMODYNAMIC AND KINETIC PARAMETERS 43
B ECONOMIC DATA 46
C THE CONVENTIONAL DESIGN OF HDA PROCESS 48
D THE MODIFIED DESIGN OF HDA PROCl'SS 65
ABSTRACT
The goal of this work was to examine a modified hierarchical procedure for the
conceptual design of chemical processes with chemical reactions. This was achieved h\
examining several designs of hydrodealkylation (HDA) of toluene to benzene process (a
benchmark case in teaching chemical process design), using the modified and the
con\ entional design hierarchies.
The con\'entional design hierarchy as described by Douglas [1] has at least two
drawbacks. First, the operation ofthe chemical reactor is not considered as a separate
step ofthe design exercise, but rather as a part ofthe recycle structure. Second, the use
of a recycle stream is pureh an economic decision that should be considered in the unit
integration step, after the basic structure ofthe process is designed. Mann and Hoo [10]
proposed a modified hierarchical design structure tor chemical processes that overcomes
these drawbacks.
Results of this study show that by applying the modified hierarchical design
structure to design the HDA process, a more economical plant is designed than one
obtained by conventional hierarchical design structure. Specifically, the plant designed
by the modified hierarchy requires 70% lower capital investment (bare module cost) and
provides an operating loss 50% smaller than that ofthe conventional design. These
economic advantages are obtained mainly due to modifications in the reactor
configurations and the elimination ofthe gas recvcle stream.
These results indicate that the modified hierarchical design structure for chemical
processes with chemical reactions proposed by Mann and Hoo [10] deserves further
examination. The results indicate the importance of considering the design ofthe
chemical reactor as a distinct step in the design exercise. The results also indicate that
the implementation of a recycle stream should be assessed on the basis of economic
considerations, rather than being an inherent part ofthe design procedure.
It is recommended to continue the investigation ofthe modified hierarchical
design structure and expand the study to include the dynamic behavior ofthe process and
the required plant-wide control stmcture. Also, it is recommended to examine the
application of the modified hierarchical design structure to ttther chemical processes with
chemical reactions.
VI
LIST OF TABLES
2.1 Comparison of textbook examples using the HDA process 6
2.2 Kinetic data for Reaction 2 from Hougen and Watson 15] 10
2.3 Ke> process streams for the conventional HDA process 15
3.1 Key process streams for the modified HDA process 25
4.1 Major equipment costs ofthe HDA processes 29
4.2 Bare module costs of major units ofthe HDA processes 30
4.3 Equipment costs ofthe HDA process 31
4.4 Bare module costs of the HDA process 32
4.5 Total grass roots plant costs ofthe HDA process 33
4.6 Benefits ofthe modified design 33
4.7 Disadvantages ofthe modified design 33
4.8 Comparison ofthe reactor design based on coiTccted rate expressions 35
B. 1 Toluene and Benzene price information [27, 28] 47
B.2 Hydrogen and Methane fuel values information [1] 47
C. 1 Conditions and compositions for all material streams ofthe conventional
HDA process 49
C.2 Parameters for equipment ofthe conventional HDA process 54
C.3 Process unit costs for the conventional HDA process 60
C.4 Operating cost summary for the conventional HDA process 64
D. 1 Conditions and compositions for all material streams ofthe modified
HDA process 66
Vl l
LIST OF TABLES (continued)
D.2 Parameters for equipment ofthe modified HDA process 73
D.3 Process unit costs for the modified HDA process 82
D.4 Operating cost summary for the modified HDA process 85
Mi l
LIST OF FIGURES
2.1 Plot of In ( k,v ) \ ersus 1/T 11
2.2 Fhe input/output structure of the conventional 11 DA process 14
2.3 The conventional HDA process 16
3.1 An "'ideal" input/output structure of HDA process 17
3.2 The input/output structure of the proposed modified HDA process 19
3.3 .A reactor with distributed side injection 20
3.4 Potential reactor configuration for the modified I IDA process 20
3.5 A plot of Hin/TLjn ratio versus reactor sections 22
3.6 The modified HDA process 24
C. 1 Temperature profile ofthe reactor in the conventional HDA process 58
C.2 Reaction rates in the reactor of the conventional HDA process 59
C.3 Component mole fraction in the reactor ofthe conventional HDA process 59
D. 1 Temperature profile of Reactor 1 in the modified HDA process 76
D.2 Reaction rates in Reactor 1 ofthe modified HDA process 76
D.3 Component mole fraction in Reactor 1 ofthe modified HDA process 77
D.4 Temperature profile of Reactor 2 in the modified HDA process 78
D.6 Component mole fraction in Reactor 2 ofthe modified HDA process 79
D.7 Temperature profile of Reactor 3 in the modified HDA process 80
IX
IST OF FIGURES (continued)
D.9 Component mole fraction in Reactor 3 of the modified HDA process 81
NOMENCLATURE
.A, reaction rate pre-exponential coefficient of i"' reaction, depend on reaction
c , molar-based specific heat of species j , BTU/lbmole-K
Eaj activation energy of i'^ reaction, energy/lbmole
EP economic potential, $/hr
Hf standard heat of formation of species j , BTU/lbmole
.AHp, ( T) heat of reaction at temperature f, BTU/lbmole
AH,, (298 K) heat of reaction at standard conditions (1 aim and 298 K). BTU/lbmole
1^2^' dimensionless reaction \elocity constant of Reaction 2
k| rate constant of i-th reaction
L/D length-to-diameter
OC operating costs. $/hr
p partial pressure of species j . psia
PR profit rate, $/lir
R universal gas constant, cnergy/lbmole-R
r reaction rate of i"' reaction, Ibmole/min-ft
s stoichiometric coefficient of species j
T temperature, depend on equation
j . ^ inlet temperature, depend on equation
X^^j outlet temperature, depend on equation
XI
ABBREVIATIONS
B benzene
CS
D
H
carbon steel
diphenyl
hN'droiicn
HDA the hydrodealkylation of toluene to benzene
M methane
P
PFR
SS
TL
pressure
plug-flow reactor
stainless steel
toluene
XII
CHAP! ER 1
OBJECTIVES AND MOTIVATION
The objective of this work is to investigate the effectiveness of a modified
hierarchical structure for conceptual design of chemical processes involving chemical
reactions. This is accomplished by examining (comparing) several designs ofthe
hydrodealk\'lation (HDA) of toluene to benzene process, using the modified and the
conventional design hierarchies. A design that yields a more economical plant (higher
profit, lower investment, etc.) is considered superior.
The conventional process design procedure consists of a hierarchical structure
described by Douglas [1]. The main elements ofthe design procedure are:
1. Selection of batch or continuous operations,
2. Identification of an input/output structure,
3. Identify a recycle structure,
4. Identify a separation structure,
5. Consideration of heat integration.
This hierarchical stmcture has at least two drawbacks. First, for process involving
chemical reactions, the operation ofthe chemical reactor is not considered as a distinct
step ofthe design exercise, but rather as a part ofthe recycle structure [1]. In most
chemical processes with chemical reactions, the chemical reactor is the "heart" ofthe
process, and its operation determines the conditions at which other units in the process
operate [11]. Second, the use of a recycle stream is purely an economic decision, and
should not be decided upon a priori, as implied from the current process design hierarchy.
In this context, a "recycle" is defined as a fraction of a stream (at the limit, the entire
stream) that is relocated, without modifying its composition to a point upstream in the
process. An alternative to a recycle is to change the composition ofthe stream (by a
separation unit) and then direct the modified (separated) streams either to storage or to
points in the process. Of course, the advantage of a recycle is that it does not involve the
additional separation step and its associated costs. However, the main disadvantage of a
recycle is that if the stream contains some species that are not removed, they build-up in
the process and this necessitates purging of a portion ofthe recycle stream, resulting in
the loss of valuable components. Only when the cost of purging the valuable components
is low. and the expense of recycling (e.g., compression) is not high, recycle is
economical. Another disadvantage of recycle is that it complicates the dynamic (non-
steady state) behavior ofthe process by adding interactions among the process variables.
This makes the synthesis of a control system much more difficult. However, this impact
is not considered in this work, which is limited to steady state design.
A modified hierarchical structure for designing chemical processes with chemical
reactions that addresses these drawbacks was recently proposed by Mann and Hoo [10].
It adds a distinct step of considering the design and operation of a chemical reactor to the
design procedure, and it moves the consideration of recycle to the unit integration step.
Hence, the main elements ofthe modified design hierarchy are:
2. Identification of an input/output structure.
3. Identify and select reactor subsystem,
4. Identify and select separation subsystem,
5. Considering unit integration to maximize profit:
a. material rec>cle management, and
b. heat integration.
The purpose of this work is to examine whether the modified hierarchical
structure for conceptual design of chemical processes provides a superior design than the
con\ entional structure. The HDA process to produce benzene from toluene was selected,
as an example to compare the two hierarchical structures because it is an instructional
case in the pedagogy of chemical process design.
The thesis is organized as follows. Chapter 2 provides a review ofthe
conventional process design hierarch\. describes the HDA process, and provides the
thermodynamic and kinetic data needed for the design. Chapter 3 describes the modified
HDA process. Chapter 4 provides an economic comparison ofthe modified and the
conventional HDA process. Chapter 5 pro\'ides a summary ofthe conclusions drawn
from this study and a list of recoiumendations for future work.
CHAPTER 2
CONVENTIONAL HIERARCHICAL DESKiN STRUCTURE
AND HDA PROCESS
2.1 Background
The design exercise has a major impact on the economics and the sustainability oi"
chemical processes. Many decisions made during the design determine the economical
performance ofthe plant, its effects on the environment, and its adaptability to changes in
market conditions. By its nature, process design is done on the basis of incomplete
information. Therefore, tlnding an efficient methodology for conceptual process design
is important.
In general, the design of chemical processes is divided into two distinct stages.
First, the process is designed for steady-state operation to meet the specified production
objectives and product purit\'. This stage leads to the formulation of a process flow sheet,
which defines all the units in the process and their connectivity. Second, a control system
is designed to maintain the specified operating conditions in spite of disturbances. The
design ofthe control system and the selection ofthe control components are carried out
after the flow sheet is completed, and these tasks are considered to be the doinain ofthe
process control engineer. This work is limited to the first stage: steady-state design and
the formulation of a process fiow sheet.
The design exercise of chemical processes has been covered extensively in the
literature, and its principles are taught in the senior year ofthe chemical engineering
curriculum. While different textbooks provide different eiuphasis on various aspects of
the design exercise [1, 2, 6, 11, 26], all of them follow the basic hierarchical structure
de\ eloped b> Douglas [1]. Howexer. because ofthe limitations indicated in Chapter 1, it
is useful to examine a modified design hierarchy to determine whether it may result in a
superior process flow sheet; i.e., in a plant that is more economical.
The h\drodealkylation (HDA) of toluene to benzene process has been used as an
instructional case in teaching chemical process design, and is extensively covered in the
literature [1-3, 6, 11-21]. In this process, hydrogen and toluene react to form benzene;
methane is formed as a by-product ofthe reaction. At the reactor operating conditions,
benzene also reacts to form diphenyl in a secondary reaction. The HDA process
encompasses the follow ing common issues that appear in many chemical processes:
1. Constraints on the proportion ofthe reactants.
Constraints on the reactor temperature.
Implementation of recycle streams,
4. Application of heat integration.
Table 2.1 provides a eoiuparison ofthe differences among several HDA flow sheets
(designs). In the design ofthe HDA process coxered in the textbooks, the design ofthe
chemical reactor is not considered in detail. In fact, in all of them, the size ofthe reactor
is calculated assuming that the reactor is ideal plug-flow, and operates isothermally
(temperature varies narrowly from 1,150 to 1,260'T). Also, in all cases, the reactor is
designed for 75% conxersion of toluene to obtain a pre-specilied yield of benzene.
1
J .
Table 2.1: Comparison of textbook examples using the HDA process
Textbook
.Author
Douglas |1]
1 urton et al. [6]
Smith [11]
Siederetal. |2]
Luyben et al. [3]
Number of
chemical
reactions
considered
1
1
1
T
1
Number of
distillation
columns
->
1
.1
Discharge of
diphenyl as a
pollutant
Considered
Not considered
C onsidered
Considered
Considered
Recycle of
diphenyl to the
reactor
Considered
Not considered
Not considered
Not considered
Not considered
2.2 Design Objectives and Process Specifications
The design task at hand is to design a chemical process to produce benzene at a
rate of 265 Ibmole/hr with a product (benzene) purity of 0.997. Two streams are assumed
to be aA ailable for the process: a gas stream containing (in mole %) 95% hydrogen and
5o methane, at a pressure of 550 psia and a temperature of lOO'T; and a liquid stream of
toluene, at ambient temperature and atmospheric pressure.
To achiexe the specified objectives, a process based on hydrodealkylation (HDA)
of toluene to benzene is considered. The following non-catalytic, gas-phase chemical
reactions take place in the process:
Reaction 1: C, H, +Hj _ C H + CH4
Reaction 2 and 3: 2CH ^ C , . H , + H,
That is, hydrogen and toluene react to form benzene and methane in Reaction 1, and
diphenyl is formed in the secondary reaction. Note that the secondary reaction is
reversible reaction, and the forward reaction is denoted as Reaction 2 and the reverse
reaction is denoted as Reaction 3. For simplicity, in the remainder ofthe thesis, benzene
(CftHft) will be denoted by B, toluene (CvHx) by TL, hydrogen (H2) by H, methane (CH4)
by M, and diphenyl (C12H10) by D.
2.3 Process Conditions and Constraints
Experimental kinetic studies indicate that the following constraints should be
imposed on the reactor operating conditions [1-3, 6, 11]:
1. To achieve satisfactory reaction rate, the inlet reactor temperature should be
maintained at 1.150'T or higher.
2. The reactor temperature must not exceed 1,300"F to prevent a significant
amount of hydrocracking.
3. The proportion of hydrogen-to-toluene at the inlet ofthe reactor should be at
least five to reduce coking.
4. The outlet stream from the reactor should be quenched.
In addition, the reactor pressure cited in the literature is 500 psia [1, 31, and it is assumed
that the reactor is operated at this pressure. In principal, the reactor pressure can be
optimized to maximize profit, but since the objective of this work is to compare the
modified design procedure to the conventional one, the stated reactor operating pressure
is used.
2.4 fhermodynamic and Kinetic Data
fo carrx out the design ofthe HDA process, thermodynamic and kinetic data are
needed. A literature survey indicates an inconsistency in the data used in the
conventional design [3]. Thus, these inconsistencies are first reconciled in order to make
the comparison ofthe modified design procedure meaningful.
The thermodynamic and kinetic data used by Lux ben et al. [3] and other
inxestigators [1,6] are inconsistent because the activation energy (Ea) of Reaction 2 was
taken to be equal to the activation energy of Reaction 3, its reverse reaction, thus
implxing that the heat of reaction of Reaction 2, AH^^, is zero. However, the heat of
reaction of Reaction 2 is not zero, as reported by Hougen and Watson [5]. Also, the
calculation ofthe heat of Reaction 2 from the heat of formation ofthe .species, based on
the thermodynamic database of H\SYS.PLANT 2.2 |25], indicates that AH^^ is not
zero.
To resolve this inconsistency and to verify all thermodynamic data, the species
heat of formations [7] and their specific heat capacities [8] are used to calculate the heats
of reaction of Reactions 1 and 2. The heat of reaction at standard conditions (1 atm and
298 K) is obtained from species heat of formation bx (see. for example. Smith et al. [29|)
AH",(298K) = Xs , H' ; , , (2-1)
J
where s is the stoichiometric coefficient of species j in the reaction. At temperature T,
the heat of reaction is.
AH, (T)=AHi ; (298K)+ j X^ i ^ P ^ T , (2-2)
where c,,^ is the molar-based specific heat of species j . Ba.sed on published
themiodynamic data [7, 8], the calculated heats of reaction of Reactions 1 and 2 are (see
detailed calculation in Appendix A):
For Reaction 1 AH; ; (298 K) =-1. 803 10' BTU/lbmole
AHR (l 150 F)=-2.096-10"* BTU/lbmole
For Reaction 2 AH',; (298 K) = 6.9X4-10' BTU/lbmole
AH,, (1 150F) = 1.118-10' BTU/lbmole.
Note that AH,, is consistent xvith the value used bx Luyben et al. [3] and others.
Hoxxex er. AH at 1.150"F is 1.118-10"* BTU/lbmole, and not zero as assumed.
The reaction rate expressions for the three chemical reactions are provided by [3]:
r, = A, exp(-l':a|/RT)pT. p, , "' (2-3)
r, = A. exp(-Ea2/RT) p^' (2-4)
r^ = A3 e.xp(-EayRT) p p,, (2-5)
where r|. ri and r3 are the reaction rates expressed in lbmole/(min-fr );P| (j = TL, H, B,
D) is the partial pressure (psia) of species j ; Ai, A2, and A; are the reaction rate pre-
exponential coefficients for Reaction 1, 2 and 3, respectively; Eai, Ea^, and Ea3 are the
respective activation energies; T is the absolute temperature; and R is the universal gas
constant.
Since the heat of reaction of Reaction 2 is not zero, the rate expressions of
Reactions 2 and 3 should be reconciled to account for the different activation energies.
To do so, the kinetic data of Reaction 2, reported by Hougen and Watson [5], are used
(see Table 2.2) to obtain the activation energx'. The reported reaction rate velocity
Table 2.2: Kinetic data for Reaction 2 from Hougen and Watson [5]
Temperature, K
644.26
699.82
755.37
Dimensionless reaction velocity constant, k^v
0.15
1.00
5.00
810.93 ' 20.00
866.48
922.04
977.59
1,033.15
70.00
200.00
500.00
1,000.00
constants at different temperatures are plotted using the Arrhenius equation.
ln(k,A' ) =
La,
RT
-I- constant
(2-6)
where k^v is the dimensionless reaction velocity constant of Reaction 2. Even though
Hougen and Watson [5] use the dimensionless reaction velocity constant rather than the
absolute value ofthe reaction rate constant, the determination ofthe actixation energx of
Reaction 2 is still possible. Using the data from Table 2.2. Figure 2.1 is generated. The
straight line has a slope equal to -Eaj/R. From the slope ofthe curve, the value of Ea./R
is 15,362 K. Now that the value of Ea2/R is known, using the relationship between the
heat of reaction and the activation energies ofthe forward and backward reactions,
AH,, =I-;a . , , - Ea_, (2-7)
10
Figure 2.1: Plot of In ( k, r ) versus 1/T
Ea3/R ofthe reverse reaction can be calculated as follows:
Ea, - Ea, = AH
(2-8)
Ea, Ea, AH,,^
R R R
(2-9)
Ea, Ea, AH,
R R R ' - - "
Appendix A provides more details on how the value of EaVR is determined. The
calculated value of Ea3/R is 12.237 K. Since the calculated values Ea2/R and Ea3/R are
different than those in the rate expressions used in the literature, consistent rate
expressions should be used in both cases. In order to match the adjusted reaction rates of
Reactions 2 and 3 (with different Lai and Lai) with the reaction rates used in the
literature, each expression was required to provide the same value at 1,150'T (the reactor
inlet temperature).
11
For Reaction 2.
A,
l.ahuMal^'-'^P
^^:(;Kl| ustcci)/R '
894.26
= 5.987-lO'e.xpl
For Reaction 3.
/\
Md,MC,l,eXP
894.26
2.553 lO'exp
Ea, / R
894.26
f E a , / R ^
894.26
(2-
(2-12)
Soix ing these expressions, the following xalues arc obtained (see Appendix A):
Ibmole
A:,, =0.62717-
A,d,s,ed,-0.08124-
min - It - psia"
Ibmole
min-ft' -psia"
Using these calculated x alues. the adjusted reaction rate expressions are:
( 2.5616-10' ^
r, = 3.6858-lO' exp
T
PTPH
r, =0.62717 exp
1.5362-10
T
4 X
r, =0.08124 exp
^ 1.2237-10"'^
T
Pn"
PD PI
(2-131
( 2- 1 4 )
(2-15)
where ri, r2, and r3 are in lbmole/(min-ft'). and T is in degrees K. and p, is in psia. These
corrected rate expressions are used, in this study, to design the reactor ofthe HDA
process.
12
2.5 The Conventional 1 IDA Design
The conx entional HDA process is designed following the design hierarchy
presented bx Douglas [1] and outlined in Chapter 1. This design is used as the base case
to xvhich the modified HDA process is compared.
.A schematic ofthe input/output structure ofthe conventional HDA process is
shoxvn in Figure 2.2. The process consists of reactor and separation systems. The
conx entional design was carried out under the assumption that the conxersion of toluene
in the reactor is 75%). Stoichiometrx indicates that Reaction 1 requires a 1-to-l
proportion of toluene and hydrogen. However, as indicated, the chemistry necessitates a
5-to-l ratio of toluene and hydrogen at the inlet ofthe reactor to reduce carbonization of
the toluene. Therefore, for each mole of benzene formed, five moles of hydrogen should
be fed to the reactor. Further, since the conversion of toluene is only 75%, for each mole
of unconverted toluene, fixe moles of hydrogen should be fed into the reactor. The
excess amount of hydrogen (aboxe the stoichiometric amount) acts as an inert, and taxes
the reactor operation by diluting the reactants. It also advocates recycling the
unconverted hxdrogen from the separator to the reactor [1]. Note that the ct)nventional
design is based on constructing a separating unit, xvhich remox es the gaseous species
from the heavier components but does not separate methane from hydrogen. The effluent
ofthe reactor contains methane (which is formed as a by-product), and since the methane
is not removed, its level grows in the recycle stream and in the reactor. Also, recxcling
methane increases the operating cost. Presence of methane at the reactor inlet reduces the
concentration of reactants (toluene and benzene) throughout the reactor. To avoid
13
H
M
Tl
^
Recycle of H and M (gas-phase)
r
i k
Reactor
System
Recycle
Separator
System
af TL (liquid-phase)
^ H
M
^ n
Figure 2.2: The input/output structure ofthe conventional HDA process
methane build-up, a portion ofthe gas recxcle needs to be purged. Note that the level of
methane in the recycle loop is a design decision based on economic considerations
(affects the amount of hydrogen purged) and safety considerations. The larger the flow
rate ofthe purge stream, a large amount of hydrogen is lost, but lower levels of methane
are recycled. The conventional HDA process is designed such that the level of methane
at the reactor inlet is around 54 mole%. This results in a hydrogen loss at a rate of about
636 Ibmole/hr in the purge stream.
The flow diagram ofthe conventional HDA process is shown in Figure 2.3. The
design ofthe conventional HDA process (see Appendix C) is accomplished using
HYSYS.PLANT 2.2 [22] and the UNIQUAC thermodynamic property package. The
design follows the information provided bx Douglas 11]. Luyben et al. | 3], and the
14
coiTected (modified) rate expressions derived in Section 2.4. The information about key
process streams for the conventional HDA process is shown in fable 2.3.
Table 2.3: Kex process streams for the conventional HDA process
Fl ow rat e,
Ibmole hr
Temper at ur e, "F
Mol e fraction
H
M
B
TL
D
Fresh
Toluene
Stream
285. 9
86
0. 0000
0. 0000
0. 0000
1.0000
0. 0000
Fresh
Hydrogen
Stream
4%. 4
86
0. 9700
0. 0300
0. 0000
(1 0000
0. 0000
Reactor
Inlet
Stream
4 382.5
1 150
0.42' ) 1
0.4800
0.0053
0. 0856
0.0000
Reactor
Effluent
Stream
4 382 5
1 263
0.3644
0.5463
0.0685
0.01^)3
0.0015
Purge
Stream
636. 8
115
0 391)2
0.5937
0.0065
0.0006
0.0000
Product
Stream
(Benzene)
265
211
0.0000
0.0000
0.9997
0.0003
0.0000
By-
Product
Stream
(Diphenyl)
6.8
559
0.0000
0.0000
0.0000
0.0003
0.9997
Gas
Recycle
Stream
3 519.2
115
0.3992
0.5937
0.0065
0.0006
0.0000
Toluene
Recycle
Stream
82.1
272
0.0000
0.0000
0. 0006
0.9994
0.0000
15
CHAPTER 3
THE MODIFIED HDA PROCESS
This chapter describes the design ofthe modified HDA process using the
modified hierarchy proposed bx' Mann and Hoo [10]. 1 he main elements ofthe modified
hierarchy are:
2. Identification of an input/output structure,
3. Identify and select reactor subsystem.
4. Identify and select separation subsystem,
5 Considering unit integration to maximize profit:
a. material recycle management.
b. heat integration.
The design goal is the same as that ofthe conventional HDA process: to produce
265 Ibmole/hr of benzene with a purity of 0.997. First, an "ideal"" input/output structure,
shown in Figure 3.1, is considered for the production of benzene only (without the
second, undesirable reaction). This represents the ideal case where all the raw materials
Toluene
Hydrogen
HDA Process
-> Benzene
Figure 3.1: An "ideal" input/output structure of HDA process
17
(toluene and hydrogen) are completely converted to produce the desired product
(benzene) xvithout formation of any by-products (methane and diphenyl). However, the
HDA process involxes three simultaneous chemical reactions with the primary (desirable)
reaction generating methane in addition to the benzene and a secondary reaction
generating diphenx I. As a result, decisions have to be made on what to do with the
diphenyl and methane, and the unconverted toluene and hydrogen. Further, from
enxironmental consideration, it is desirable not to discharge the diphenyl and unconxerted
toluene (liquid products) from the process. Thus, the fust modification proposed is to
recycle the diphenyl and unconx erted toluene to the reactor inlet. Note that the
undesirable reaction (Reaction 2) is rexersible, and the diphenyl can be converted to
benzene if its concentration in the reactor increases. Hence, the diphenyl can be recycled
to extinction as pointed out bx' Douglas [1]. However, although the benefits of recycling
the diphenyl have been recognized in the literature, the standard design case ofthe HDA
process does not incorporate diphenyl recxcle.
The second proposed modification to the conx entional process involves the design
ofthe chemical reactor such that the amount of excess hydrogen fed to the reactor is
smaller xvithout \iolating the hydrogen/toluene ratio of 5:1 at any point in the reactor.
.Assuming this is achievable, the flow rate of recycled hydrogen can be substantiallx
reduced, and consequently, the problem of methane build-up is mitigated. As a first
design alternative, a process xvith no gas recycle, shown schematically in Figure 3.2, is
considered. Comparing this modified process to the conxentional one (Figure 2.2), note
that no diphenyl is being discharged from the process, eliminating potential
18
enxironmemal problems. .Also, the elimination ofthe gas recycle stream provides
potemial economic advantage in eliminating a large component ofthe capital
(compressor) and reducing the operating cost ofthe process.
cost
II
M
Tl
i
i
Reactor
System
Separator
System
Recxcle of TL and D (liquid-phase)
^ H
M
^ rt
Figure 3.2: The input/output structure ofthe proposed modified HDA process
In order to implement the HDA process shown schematically in Figure 3.2. it is
necessarx to identify a reactor configuration that does not restilt in the discharge of a
large amount of unconverted hydrogen. Traditionallx. the selection ofthe reactor
configuration has been done solely on the basis of maximizing the yield ofthe desirable
product (see, for example. Smith [11], Douglas [1], Levenspiel [25]). However, in
general, maximizing the yield does not necessarily correspond to maximizing
profitability. As indicated in Chapter 2, the dominating factor that affects the economics
ofthe HDA process is the large amount of hydrogen that should be fed (and recycled) to
the reactor. The key challenge in designing the reactor is:
19
Maintaining a - > 5 ratio imposed by the chemistry at each point in the
reactor, while minimizing the excess amount of hydrogen fed.
The modified reactor configuration is based on injecting the toluene along the
reactor as it is being consumed, rather than feeding the toluene at the reactor inlet (see
Figure 3.3). This is potentially achievable since Reaction 1 is exothermic, and complete
conversion of toluene is possible in excess hydrogen. To assess this reactor
TL,n
Figure 3.3: A reactor with distributed side injection
configuration, consider first that the reactor is divided into n sections, and the same
amount of toluene is injected into each section, TLm/n, as shown in Figure 3.4.
TL,n _
Hj n
TL,n/n
Section
n=l
TL,/n
Section 2
n=2
TL,/n
Section n
Figure 3.4: Potential reactor configuration for the modified HDA process
To estimate the required total flow rate ofthe hxdrogen into the reactor (H;,,).
consider first the ideal ease, xx hen only Reaction 1 occurs. It is also assumed that the
toluene, which is the limiting reactant, is completely converted in each section ofthe
reactor. From stoichiometrx, the molar flow rate of hydrogen at the inlet ofthe n"^
section is
H =H,
TL,. (3-1
V n
The inlet to the n-th section is the point in the reactor with the lowest H/TL ratio. The
imposed hydrogen-to-toluene ratio at the inlet ofthe n"' section ofthe reactor is
(n-\\
H V n j
TL TL
n
TL,
>5 (3-2)
From Eq.(3-2). Hm'TLin relationship is derived
H, 4 + n
^ ^ (3-3)
Note that as n> co . Hj|,/TLjn ratio goes to 1, which is the stoichiometric proportion of
hxdrogen and toluene in Reaction 1. Therefore, in principle, hydrogen and toluene can
be fed to the reactor in stoichiometric propoilions if a reactor xxith continuous side
injection is used (see Figure 3.3). Using Eq.(3-3). a plot of H,/TLin ratio versus the
number of reactor sections is constructed and shown in Figure 3.5. The figure shows
how the required total hydrogen feed can be reduced and how many reactor sections are
needed to achieve it. Note that the largest reduction in the Hin/TLi,, ratio occurs when the
reactor is divided into two or three sections. When only three sections are used, the
Hin/TLin ratio is reduced bx more than 50%.
5 7 9 11
n (number of reactor sections)
13
15
Figure 3.5: A plot of Hin/TL,,, ratio versus reactor sections
In designing the modified HDA process, it was assumed that each section ofthe
reactor is operated adiabatieally. and is described by a plug-flow reactor (PFR) model [4|.
From practical engineering perspectixe. this model holds for fully developed turbulent
flows XXhen the length-to-diameter (L/D) proportion is greater than 20 [4]. The inlet
temperature of each section is maintained at 1,150''F, and at any point in each section, the
temperature is not allowed to exceed 1,300'T, the highest allowable temperature imposed
by the chemistrx. Note that these are steady state operating conditions, but do not
consider dynamic (non-steady state) variation ofthe temperature.
11
The reactor is designed for the three simultaneous reactions, and various level of
diphenyl in the reactor inlet. The different cases are assessed according to the following
criteria:
1. Smallest overall reactor size that provides complete conversion of toluene in
each section ofthe reactor.
2. Keep the production of diphenxi at a loxv level.
3 Keep the production of benzene at a high level.
4. Operate the reactor at temperatures close to 1.300"F.
The reactor design equations were solved using HYSYS.PLANT 2.2 [22] and the
solutions checked by using the numerical method software LliQ" [23]. Reactors with
txxo, three and four sections are considered. Studies show that a reactor with three
sections provides a configuration with the smallest oxerall reactor xolume, and loxx
diphenyl flow rate.
After the reactor is designed, it is incorporated into the design ofthe HDA process
using H\'SYS.PLANT 2.2 [22]. Details ofthe design are provided in Appendix D. The
HDA process xx ith the modified reactor system is shown in Figure 3.6. and the kex'
process stream information is provided in Table 3.1.
(U
o
X
-a
-5
OJ
3
OB
24
Table 3.1: Kex process streams for the modified HDA process
Flow rate,
Ibmole/hr
Temperature, "F
Mole fi-action
H
M
B
TL
D
Fresh
Toluene
Stream
269
86
0.0000
0.0000
0.0000
1.0000
0.0000
Fresh
Hydrogen
Stream
665.6
86
0.9700
0.0300
0.0000
0.0000
0.0000
Total
Reactor
System
inlet
976.8
1175
0.6609
0 0204
0.0000
0.2853
(1.0333
Reactor
Effluent
Stream
976.^)
1300
0.3856
0.2')5S
0.2753
0.0100
0.0333
Purge
Stream
656.3
80
0.5723
0 4240
0.0037
0.0000
0.0000
Product
Stream
(Benzene)
265.1
167
0.0000
0.0002
0.^)')^)7
0.0001
0.0000
Toluene and
Diphenyl Recycle
Stream
42.2
1168
0.0000
0.0000
0.0001
0 2293
0.7706
25
CHAPTER 4
ANALYSIS: COMPARISON OF THE MODIFIED AND
THE CONVENTIONAL DESIGNS
4.1 Economic Potential and Profit Rate
In general, ex erx design of a chemical process is assessed on the basis ofthe
economic feasibilitx ofthe final process. Hence, to compare the modified and
conventional design procedures, an economic assessment is carried out for each, and then
compared. For each case, an economic potential is done in each stage ofthe design
exercise.
Since the prices of chemical species vary, to determine the economic potential,
fixed X alues are assigned to each reactant and product. The prices are taken from
Chemical Marketing Reporter for December 2001 (see Appendix B). Values ofthe
hydrogen and methane in the purge stream are taken as their heating values, as was done
by Douglas [1].
The first step in evaluating the economic feasibilitx of a chemical process is to
conduct a simplified economic potential (EP) - how much profit can the process
generate. For the input/output structure, the economic potential is defined by
all products
Product
flow rate,
Ibmole/hr
Product
value,
$/lbmole
z
all law inalenais
Reactant 1
flow rate,
Ibmole/lir
Reactant "i
value,
$/lbmole^
(4-
where EP indicates the potential profit the process can generate, expressed in $/hr. The
comparison ofthe modified and conventional HDA designs begins with an evaluation of
26
their economic potential using the input/output structures (Figures 2.2 and 3.2.
respectivelx). the associated species flow rates (see Appendices C and D). and the species
prices (see Appendix B).
For the input/omput structure ofthe HDA process, the economic potential is given
bv.
EP =
Benzene V <
^ Value of ^
Production
Rate,
Ibmole/hr
^Diphenyl ^
Flow
Rate,
Ibmole/hr,
Benzene,
$/lbmole
V
^ Value of ^
Diphenyl,
$/lbmole J
+
Purge
Floxv
Rate,
Ibmole/hr
^ Value of ^
Purge,
$/lbmole
^Toluene ^
Feed
Rate,
Ibmole/hr
^ Value of ^
Toluene,
$/lbmole
'^ Hydrogen y Value of ^
(4-2)
/
Feed
Rate,
Ibmole/hr
) \
Hydrogen
Feed,
$/lbmole
Substituting values ofthe conventional design (Figure 2.2) into Eq.(4-2) gives an EP of
- 400 $/hr. Note that the EP is negative, indicating that the process is not economically
feasible at the prevailing prices ofthe products and raw materials. It should be
mentioned that, from an economic perspective, when the EP is negative, an engineer
should look for other design alternatives to achieve the specified process design
objectives. Hoxxexer. the purpose of this xxork is to compare the conventional HDA
design with the modified design, and this can be done ex en though the economic
potential is negative. Substituting values for the modified design (Figure 3.2) into
Eq.(4-2) gives an EP of - 482 S/lrr. Hence, based on input/output stmcture alone, the
modified design is slightly less economical than the conventional design.
27
The next level of an economic assessmem incorporates the operating cost (OC).
The profit rate (PR) of a process is defined bx
PR($/hr)= EP($/hr)-OC($/hr). (4,3,
The operating cost consists ofthe expenses related to operating the process and includes
utility, labor, and maintenance [6]. In the early stages of a design exercise, only the main
utility costs are considered. A more accurate PR is calculated as the process flow sheet is
dexeloped and the operating costs ofthe individual unit operations are defined.
Considering the conxemional HDA process (Figure 2.3). the utilitx cost (power
and energx requirements), calculated by HYSYS.PLANT 2.2 [22] and presented in
Appendix C. is 1,040 $/hr. Hence, using Eq.(4-3). the calculated profit rate for the
conventional HDA process is -1.440 $/hr. For the modified HDA process (Figure 3.6).
the utility cost, as calculated by HYSYS.PLANT2.2 [22] and presented in Appendix D,
is 260 $/hr. Hence, the profit rate ofthe modified HDA process is -742 $/hr. Note, the
loss rate ofthe modified process is about 50% smaller than the loss rate ofthe
conventional process.
4.2 Capital Cost Investment
The next element in assessing the economic viability of a chemical process is
to estimate the cost of construction. The capital cost is used to determine the return on
investment and is amortized to determine a realistic profit rate. The equipment cost is
calculated using a common procedure, described, for example, by Turton et al. [6]. The
equipment cost is determined for a tabulated unit of known size, and then, the cost is
28
adjusted bx- a scaling factor. Also, the tabulated values, which are given for a specified
date, are corrected to the cuiTent cost using a cost index.
Different equipment costs are defined and used in the literature, fhe first one is
the cost of manufacturing the equipment at the manufacturer location. Table 4.1 provides
a comparison ofthe major equipment costs for the txxo designs. Note that the cost ofthe
main units for the modified design is about 4()"(i lower than that ofthe conventional
design.
Table 4.1: Major equipment costs ofthe HDA processes
Equipment
1 Heat exchanger
2 Furnace
"> Reactor sx stem
4
5
Separation sx stem
Recycle coinpressor
Total
Modified Design
$41,833
$ 109,961
$ 195,000
$ 164,045
N/A
$ 510,839
Conventional Design
$ 167,332
$209,451
$ 51.490
$ 320.240
$ 83,585
$ 832,098
The next equipment cost is called the "bare module cost" [6], indicating the cost
ofthe installed unit in the plant. It usually refers to the cost of making small-to moderate
expansions or alterations to an existing facilitx. Bare module cost includes both direct
and indirect costs. The direct cost consists of equipment (f o.b.) cost, materials required
for installation, labor to install equipment and material. The indirect cost includes
freight, insurance, taxes, construction overhead, and contractor engineering expenses.
Table 4.2 shows the comparison ofthe major bare module costs betxveen the txvo HDA
process designs. Note that the total bare module cost ofthe modified process is about
65%) lower than that ofthe conventional process.
29
Table 4.2; Bare module costs of major units ofthe HDA processes
1
">
3
4
5
Eciuipment
Heat exchanger
Furnace
Reactor sx stem
Separation system
Recycle compressor
Total
Modified Design
$ 286,547
$415,655
$ 220,000
$ 609,645
N/A
S 1,531,847
(-'onventional Design
$ 1,146.188
$791,724
$912,985
$ 1,399,198
$226,619
$4,476,714
Tables 4.3 and 4.4 prox ide a comparison ofthe detailed equipment costs and bare
module costs for the txxo designs. Note that \xhen considering all the elements ofthe
HDA process, the total bare module cost ofthe modified design is about 70% lower than
that ofthe conventional design.
Another cost estimate commonly used is the grass roots plant cost [6]. It refers to
the cost of a new facilitx, where the construction starts on essentially undeveloped land (a
grass field). Table 4.5 shows the total grass roots plant costs comparison for the modified
and the conventional HDA processes. Note that if the HDA process is constructed, the
cost ofthe modified process is about 57% ofthe cost of a conventional plant.
Table 4.3: Equipment costs ofthe HDA process
1 1
2
3
4
5
6
7
Equipment
-êed Pump
-leat Exchanger
-urn ace
Reactor(s)
Cooler
Separator
Stabilizer Column
8 iProduct Column
9 Recxcle Column
10 IRecxcle Pump
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Recycle Compressor
Separator
Separator
Heat Exchanger
Heat Exchanger
Heater
Heater
Cooler
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Total
Modified Design
Label (Figure 3.6)
P-101
E-lOO
Furnace
PFR-100, PFR-101,
PFR-102
E-103
V-100
N/A
T-1 GO
N/A
P-100
N/A
V-102
V-101
E-105
E-106
E-101
E-102
E-104
For Column T-100
For Column T-100
For Column T-100
N/A
N/A
N/A
N/A
N/A
N/A
Cost
$ 20.432
$41,833
$ 109,961
$ 195,000
$37,584
$ 16,931
N/A
$31,542
N/A
$ 11.920
N/A
$ 12.129
$ 2,300
$ 13,152
$ 8,860
Included in
Furnace
Included in
Furnace
$ 16,843
$ 16,112
$21,066
$9,538
N/A
N/A
N/A
N/A
N/A
N/A
$ 565,203
Conventional Design
Label (Figure 2.3)
P-100
E-lOO
E-101
PFR-lOO
E-102
V-lOO
T-102
T-100
r-101
P-lOl
K-lOO
N/A
N/A
N/A
N/A
N/A
N/A
N/A
For Column T-100
For Column T-100
For Column T-100
For Column T-102
For Column T-102
For Column T-102
For Column T-101
For Column T-101
lor Column T-101
Cost
$ 20,432
$ 167.332
$ 209,45 1
$51,490
$26,471
$58,219
$35,920
$62,059
$ 22.892
$ 17,108
$83,585
N/A
N/A
N/A
N/A
N/A
N/A
N/A
$ 16,112
$21,066
$9,538
$ 9,980
$ 19,452
$9,538
$7,329
$ 12,126
$9,538
S 869,638
31
Table 4.4: Bare module costs ofthe HDA process
1 1
2
3
4
5
6
Equipment
êed Pump
-leat Exchanger
"urnace
êactor(s)
Cooler
Separator
7 Stabilizer Column
8
9
10
11
12
13
14
15
16
17
18
19
20
21
-n
23
24
25
26
27
Product Column
Recycle Column
Recycle Pump
Recycle Compressor
Separator
Separator
Heat Exchanger
Heat Exchanger
Heater
Heater
Cooler
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Total
Modified Design
Label (Figure 3.6)
P-101
E-lOO
Furnace
PFR-lOO, PFR-101,
PFR-102
E-103
V-lOO
N/A
T-100
N/A
P-lOO
N/A
V-102
V-lOl
E-105
1-.-106
E-101
E-102
E-104
For Column T-100
For Column T-100
For Column T-100
N/A
N/A
N/A
N/A
N/A
N/A
Cost
$ 67,628
$286,547
$415,655
$ 220.000
$ 130.915
$ 95,623
N/A
$ 133,107
N/A
$ 39,454
N/A
$ 37,479
$7,107
$45,811
$30,861
Included in
Furnace
Included in
Furnace
$55,581
$53,169
$ 65,094
$31,570
N/A
N/A
N/A
N/A
N/A
N/A
$ 1,715,601
Conventional Design
Label (Figure 2.3)
P-100
E-lOO
E-101
PFR-lOO
L-102
V-lOO
T-102
T-100
T-101
P-101
K-lOO
N/A
N/A
N/A
N/A
N/A
N/A
N/A
For Column T-100
For Column 1-100
For Column T-100
For Column T-102
For Column T-102
For Column T-102
For Column T-101
For Column T-101
For Column T-101
Cost
$ 67,628
$ 1,146,188
$791,724
$912,985
$ 89,563
$419,924
$ 196,385
$216,767
$ 73,208
$ 56,626
$226,619
N/A
N/A
N/A
N/A
N/A
N/A
N/A
$53,169
$ 65,094
$31,570
$ 32,934
$ 82,087
$31,570
$24,185
$ 51,172
$31,570
$ 4,600,968
32
Table 4. 5: Total grass roots plant costs oft he HDA process
Total Grass Roots Plant Cost
Modified Design
S 2,733,000
Conventional Design
$ 6,337,000
4.3 Performance Comparison
. \t this point, it is xxorth highlighting the key benefits and disadvantages oft he
moditied HDA design ox er the conventional one. It is also interesting to examine where
the main economic benefits oft he modified process arc derived. Table 4.6 provides the
main benefits of t he modified design, and Table 4.7 highlights the drawbacks oft he
modified design.
Table 4.6: Benefits oft he modified design
Reactor volume, ft
Feed rate to separator svstem, Ibmole/hr
Compressor power, hp
Stabilizing column
Toluene/Diphenyl distillation column
Profit, $/hr
Grass roots cost ofthe plant, $
Modified Design
2,092.3
974 .5
N/A
N/A
N/A
-74 2
2,733,000
Conventional design
4 ,74 3.5
4 ,4 05.9
1!
Needed
Needed
,4 4 0
6,337,000
Table 4.7: Disadvantages oft he modified design
Total purge rate, Ibmole/hr
Total hydrogen purged, Ibmole/hr
Modified
HDA Process
669.4 6
376.54
Conventional
HDA Process
495.38
206.08
From Table 4.6. the modified design provides the following advantages over the
conventional process:
1. Profit is 50"0 higher (loss is 50" smaller).
2. Required reactor volume is 56" d smaller.
3. Size of separation sxstem needed is 78"/o smaller.
4. Investment is 43"lower.
The only disadx antage ofthe modified process is the higher rate of discharge of
unconverted hxdrogen from the plant (376.5 Ibmole/hr \ersus 206.1 Ibmole/hr). From
Table 4.7, the modified process discharges about 170 Ibmole/hr of hydrogen more than
the conventional process. Hoxxex er, the discharge stream is richer in hydrogen (56.2
mole% versus 41.6 mole%). xvhich makes it a more attractive candidate for hydrogen
recoxerx' (see discussion in Chapter 5). Note that exen though the modified HDA process
purges more hydrogen than the conventional process, it is more economical because it
does not recycle a large gas stream, and the compressor is no longer required. The
compressor represents about 10"/o ofthe equipment cost and about 5% ofthe bare module
cost.
The modified reactor configuration (injecting toluene in the reactor as it is
consumed) enables the designer to obtain the same production rate in a smaller reactor
volume in comparison to the conventional plug-fiow reactor configuration. In addition,
by eliminating the gas recycle stream and the corresponding dilution by methane, the rate
of Reaction 1 is higher in the modified HDA process than in the conventional process
(see Appendices C and D). Since the toluene is injected at the inlet of each section, the
inlet temperatures of sections 2 and 3 can be above 1,150"F, using the energy from
Reaction 1 to achiex e higher reaction rate. The modified reactor configuration simplifies
the rest ofthe process design in comparison to the conventional design (the recycle
column and the recx cle compressor arc not necessary).
One additional poim should be examined. Since corrected reaction rate data are
used in the design ofthe modified HDA process, it is necessary to examine whether the
Table 4.8: Comparison ofthe reactor design based on corrected rate expressions
Heat of Reaction 1, BTU/lbmole
Heat of Reaction 2, BTU/lbmole
Activation Energy of Reaction 1, cal/mole
Activation Energy of Reaction 2, cal/iuole
Activation Energy of Reaction 3, cal/mole
Pre-exponential reaction rate coefficient
of Reaction 1. lbmole/min-ft3-psial.5
of Reaction 2. lbmole/min-ft3-psia2
of Reaction 3. lbmole/min-ft3-psia2
Toluene flow rate from the reactor,
Ibmole/lir
Hydrogen flow rate from the reactor,
Ibmole/hr
Benzene flow rate from the reactor,
Ibmole/hr
Diphenyl flow rate from the reactor,
Ibmole/hr
Methane flow rate from the reactor,
Ibmole/hr
Reactor Volume, ft3
Conventional HDA
process xvith the
reaction rates used by
Luyben et al. [3]
-2.150e+04
0
5.09e+04
5.09e+04
5.09e+04
3.69e+06
5.99e+04
2.55e+05
90.64
1,704.26
290.64
4.09
2.282.17
4,743.48
Toluene conversion, % I 75
Conventional
HDA process
xvith the adjusted
reaction rates
-2.108e+04
1.05e+04
5.09e+04
3.05e+04
2.47e+04
3.69e+06
0.6272
0.1011
127.81
1,729.61
289.30
1.8
2,257.37
4,743.48
75
3>
benefits ofthe modified design are due to the different xalues ofthe rate parameters used
and not due to the design itself To examine this, the conventional process was designed
xxith the reaction rates used in the literature (for example, in Luyben et al. [3]) and the
adjusted reaction rates (see Chapter 2). Table 4.8 presents the design ofthe conventional
HDA process obtained using HYSYS.PLANT 2.2 [22] when both sets of rate expressions
are used. .Vn examination t)f the xalues in the table rcxeals that the reactor size and the
main stream fioxv rates in both cases are almost the saiue. It can be concluded that the
difference betxx een the modified and the conx entional designs is due to the difference in
the designs and not in the reaction rate parameters.
36
CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
Based on the results obtained in this study, several conclusions can be drawn.
Considering the hierarchical structure of ct.nceptual process design, it can be concluded
that
^ For chemical processes involving chemical reactions, the
design ofthe chemical reactor should be considered as a
separate step in the design exercise. This is consistent with
the design structure proposed by Smith |6].
-^ The use of a recycle stream should be assessed on the basis
of economic considerations rather than an inherent part of
the design procedure.
These results indicate that the modified hierarchical design structure for chemical
processes with chemical reactors proposed by Mann and Hoo [10] deserves further
examination. Considering the design ofthe HDA process, it can be concluded that
^ The modified HDA process is much more economical than
the conventional HDA process. Specifically, it requires a
70% lower capital investment for construction (bare
module cost), and it provides an operating loss 50% smaller
than the conventional process.
37
^ These economic adxantages are obtained mainly due to
modifications ofthe reactor configuration, and the
elimination ofthe gas recxcle.
It is recommended to continue the investigation ofthe modified hierarchical
strucmre for the design of chemical processes with chemical reactions. Specifically, it is
recommended to:
Lxpand the study to consider the dynamic behavior of a
process and the design of a plant-wide control structure [29].
This is an essential part of process design, since a design that is solely based on steady-
state considerations (as done in this study) docs not assure the operability and
controUabilitx ofthe process. It is also recommended to
Examine the application ofthe modified hierarchical design
structure to other chemical processes with chemical reactions.
Such examinations are necessarx to further x'alidate the modified design procedure and to
proxide insight into additional potential modifications that may be useful.
One possible xariation of both the conventional and moditied HDA processes is
adding a unit to separate the methane from the hxdrogen prior to recxcling. Recycling
the unconverted hydrogen in the gas recycle stream xvithout removing the methane from
it is not desirable due to the fact that methane does not participate in the primary reaction
(Reaction 1). This requires larger reactor volume to pass the methane through the
reactor. In the conventional HDA design, the methane ce)mposition at the reactor inlet is
more than 50"/o (by inolc). As a consequence, this will lead to a larger separation
38
subsystem. Hoxvex'er, recycling the unconverted hydrogen is possible if hydrogen is
purified to the same composition as the feed hxdrogen stream (95%). This can be
achiexed by applying membrane separation unit to separate the hydrogen from the
methane since the high-pressure (about 400 psia) purge stream is available. Note that the
high-pressure purge stream in the modified HDA design is richer in hydrogen in
comparison to the conventional HDA design. This additional design modification is not
considered in this xxork since the objective was to compare the modified HDA process to
the conx'entional one. It is recoinmended to extend the analysis ofthe HDA process to
designs that include a hydrogen recox cry unit.
39
BIBLIOGRAPHY
1. Douglas, J. M., Conceptual Design ol Cliemical I'roccs.sc.s. New York: McGraxx-
Hill(1988).
2. Seider W D., Seader .1. D.. Lcxxin D. R.. Procc.s-.s Design Principles: Synthesis.
.Analysis, and Evuliialion. New York: .lohn Wiley & Sons, Inc (1999).
3 Luyben, W. L., Tyreus B. D., Luyben M. L., Plunnvide Process ('onlrol. New
York: McGraw-HiU (1998).
4. Mann. U., Principles ofi 'hciuical Reactor Analysis and Design. Lubbock, Texas:
Plains Publishing Company (1999).
5. Hougen O. A., Watson K.M. ('hemical Process Prniciplcs: Purl 111. Kinetics and
Catalysis. Nexv York: Wilex' (1947).
6. Turton R., Bailie R. C, Whiting W. B.. Shaeiwitz J. A., Analysis. Synthesis, and
Design of Chemical Processes. Upper Saddle River, NJ: Prentice Hall, PTR,
(1998).
7. Union Carbide Corporation, Basic plwsical properties of pure organic compounds.
Laboratory manual. Volume 40-19 (1976).
8. Reklaitis G. V., Introduction to .Material and Energy Balances. New York: John
Wiley & Sons, Inc. (1983).
9 Peters M. S., Timmerhaus K. D., Plant Design and Economics for ('hemical
Engineers. Fourth Edition. New York: McGraw-Hill. Inc. (1991).
10. Personal communication. Chemical Engineering department, Texas Tech
University, Lubbock, Texas. (September 2002).
11. Smith R., Chemical Process Design. New York: McGraw-Hill (1995).
12. McKetta J. J.. Encyclopedia of Chemical I'rocessnig and Design, vol.4. New
York: Dekker (1977).
1 3 Silsbv R I Sawyer E. W., "The Dealkylation of Alkyl Aromatic Hydrocarbons I.
The Kinetics and Mechanism of Toluene Decomposition m the Presence of
Hydrogen," J. Appl. Chem., 6: 347 (August 1956).
40
14. Betts \\'. D., Popper F.. Silsbx R. 1.. -fhe Dealkvlation of Alkyl Aromatic
Hydrocarbons If-fhe Dealkylation of Coal l ar Naphthas." J. Appl Chem 7-497
(September 1957).
15. Zinmierman C. C., York R., "Thermal Demethylation of Toluene " l&EC Proc
Des. Dev.. 3: 254 (July 1964).
16. Douglas J. M., "A Hierarchical Decision Procedure for Process Synthesis " AlCliE
J, 31: 353(1985).
17. Douglas J. M., \\\)odcc)ck D. C.. "Cost Diagrams and the Quick Screening of
Process." l&EC Proc. Des. Dev.. 24: 970 (1985).
18. Terill D. L. and Douglas J. M., "1 leat E.xchanger Network Analysis.
1.Optimization." l&EC Research. 26: 685 (1987).
19. Rase H. F., Chemical Reactor Design for Process Plants, vol. 2: ('ase Studies and
Design Data New York: Wilex (1977).
20. .Andrecox ich M. J., Westerberg A. W.. "A Single Method on Utilitx Bonding for
Heat-Integrated Distillation Sequences" AlChE J.. 31: 363 (1985).
21. Vang V D., Biegler L. T., and Grossmann 1. L.. "Simultaneous Optimization and
Heat Integration xvith Process Simulation" Paper no. 72b. 1986 Annual AlChE
Meeting, Miami Beach. November 1986 submitted to Computers in Chemical
Engineering.
22. Hyprotech Ltd., HYSYS.PLANT 2.2. process simulation software, (2000), Calgary,
Canada.
23. National Instruments. HiQ numerical softxxare. (1998). Austin, Texas, USA.
24. Turton R., Bailie R. C. Whiting W B., Shaeiwitz J. A., .-inalysis. .Synthesis, and
Design of Chemical Processes. New .lersex': Prentice Hall, PTR, Upper Saddle
River (1998). attached software.
25. Levenspiel O., ('hemical Reaction Engineering. New \ork: John Wiley & Sons,
Inc. (1999).
26. Biegler L. T.. Grossmann 1. E., Westerberg A. W.. .Systematic .Methods of
Chemical Process Design. New .lersex: Prentice Hall, PTR. Upper Saddle River
(1999).
27. Chemical Marketing Reporter, December 24. 2000.
41
28. Perry's Chemical Engineer's Handbook, Seventh Edition, McGraw-Hill, NY
(1996).
29. \'asbinder li.M.. Hoo K..\.. ".\ Decision-Based Approach to Plantwide Control
Structure Synthesis." In press, Ind. Eng. Chem. Res. (2003).
42
APPENDIX A
CALCULATION OF THERMODYNAMIC AND
KINETIC PARAMETERS
43
This program calculates the thermodynamic and kinetic
adjusted parameters for the HDA process.
I nput
ill format i ou:
From Figure 3. 1 (Chapter 3 ot t h i s work), we have t he following val ue:
Ea 2 / R v a l u e , d e g r e e K:
1 S 3 6 2 e + 0 4
From Luyben et al . ( 31:
E a l / R v a l u e , d e g r e e K:
A2, I b mo l e / ( mi n f t 3 p s i a 2 )
A3, I b mo l e / ( mi n f t 3 p s i a Z )
2 5<jl<.>e + 0 4
5 9 8 7 e + 0 4
2 . .55;3e-t 0 5
2 5616e- t 0 4
2 ?. bl 6eH - 04
Push t he green arrow t o
c a l c u l a t e t he adj us t ed val ues .
Re s ul t s ( adj us t ed val ues ) of t h i s program:
He a t of R e a c t i o n 1,
B t u / I b mo l e :
2 096e+4
(From Luyben et a l . I 3 ] , t h i s
value i s -2.1S0e+04 Etu/lbmole)
He a t of R e a c t i o n 2 ,
B t u / I b mo l e :
1 1 1 8 e + 4
(From Luyben et a l . l 3 ) , t hi s
value i s 0 Btu/lbmole)
Al , I b mo l e / ( mi n f t ' 3 p s i a - " 1 . 5 )
A2, I b mo l e / ( mi n f t ^ 3 p s i a ' - Z ) .
A3 , I b mo l e / ( mi n f t / - 3 p 3 i a ^ 2 ) :
1
2 2 3 7 e + 0 4
3
6 8 5 8 e + 0 6
0 U21L1
0 0 8 1 2 4
44
d 0
dB
dT
<m
dH
1. 42a - 7;
- - 2 . 0 8 e - 6 ;
- 2 . 2 9 8 - 6 ;
= - 2 . 6 4 a - 7 ;
- i . 0 6 e - 7 ;
at> " 3 - 9 8 e - l l ;
eB - i . OSe - 9 ;
eT - l - 1 4 a - 9 ;
eM 8 . 0 1 e - l l ;
aH - i . 9 2 e - l i
The following is the program script for calculating the adjusted kinetic and
themiodynamic parameters of reaction rate expressions using HiQ^' [23].
// WotrftioH.- Baasaj M (B) / l>l,stbaiis iM) , Toluszx i' O,- Hy,Jirot,t?n (H).- Dxph&nyl (Z
/ / Ra a c t i o n 1: T V- H -->- B < M
// ^?toic>ix<?ais4ric coefficients f-rjr Rdot j o 1 .ii-:
s Tl - 1 ; s Hl - - 1 ; s Bl 1 ; slU - 1;
/ / R&.actzoiri 2: 2 B > D + H
sHZ 1; sBI -2, - sDE = 1,-
/ / H<ait o f .'î.-raaSion (Ht) j t 25 d9-i- C i n Jr<5d 1/ t t o2 f r oa "aASJC PHFSrOl i FROFSRTISS OF PURS
/ / ORSSKIC COMTOUNDS" (J,Jii>ot-,itary J>liliM,i2, Volume -10-19-1976, UtHION CASSIDS)
Ht_B 1 9 . 8 2 ;
Hf_H = - 1 7 . 8 8 9 ;
H_T = 1 1 . 9 S ;
H_H 0 ; / / It zs et^,3l to z-Bro 2>y d&fi.siitioi2.
Ht_D - 4 3 . SZ;
/ / Hs^t of Rejctioa 1 (d&lt^SRl_Z9SJ aMd P.&actl.c.-3 2 (dltaSR2_ZSS) jit 2S asg-retn C in Jôul^/^nale
dell:.aH.l_29S (sTl *Hf_T + sHl*H_H + sBl*H_B + sHlH_H) 418S. 8;
del t aHI l 2_Z98 " (sH2H_H + sB2''H_B + sD2Hf_D) *418S. 8;
,^/ ld&3il ^^5 ^Ât cutDâtt3 ,3-, h" -^-. cJ~. &~.:o&tt'lc.rer2ts
/ / J'ois.T Wzlsy i S.~f2.s, I n c . IS*-.? ipp-Ctl-itS)
aH - - 8 3 . 2 ; bC ^ 1. 02S02; cD = - 7 . 2 2 a - 4 ;
aB = 1 8 . S ; bB - - 1 . 1 7 e - 2 ; cB 1 . 2 Sa - 3 ;
a t 3 1 - S ; bT - 1 . 6 ; e ~ 2 ; cT = 1. 448- 3,
aM 3 3 . 4 ; bH - 7 . 3 7 a - i ; cH = 2 . 9 1 e - 4 ;
aH 1 7 . 6 ; bH . 7 0 e - 2 ; cH - 1 . 3 1 e - 4 ;
/ / Hedit cf R&^ctio:.!^ afc s pe oi f i e c ? t eaperd!*ui rs i .?'<?Kl/aiol
/ / .St r 894. ii K niSO F)
de l t a HRl _894 = de l t a HRl _298 t i n t e g r a t e ( c P l , 2 9 3 - I S, 894. i S , t r<i>eoi-') ;
/ / ^be f'o2 2 oi^-xi^^r v^ltts i s xn Bfe2.t/2h'Jc>2
d e l t a HRl _ Bt u l b a o l e - del t aHAl _894 <9 . 478171i 20313e- 4 j / 2 . i 046226218Se- 3 ;
f u n c t i o n c P Kx )
p r o j e c t s T l , s Hl , s Bl , s Hl , a l , aH, aB, aH, bT, bH, bB, bH, cT, cH, oB, cH,
dT, dH, dE, dH, eT, eH, eB, sH;
y = sTl-' CaT + bT*t: + C T ' K ' Z + dT>-!;'-3 + aT*x-4) +
EHl *(aH + bH' x + cH' ::' -2 + dH':t-^3 + eH-x"4) +
s Bl ( aB + bB*i! + cB' x' - ^ + dB*x"3 + eB-*x'-4) +
s Hl î aH + bH*x + cH' x--2 + dH*x' ' 3 + eH' ' x~4) ;
r e t u r n y ;
e nd a i c t i on;
// At T ^ 834.26 K (IISO F)
del t aHR2_894 dal t aHR2_298 + i n t e g r a t e I cP2, 2 9 8 . 1 5 , 8 9 4 . 2 6 , <t;r.ii>er.oi.i J ;
/ / t i j fclloiviav v a i a e zs ia Btu/li>aole
del t aHR2_Beul l . mol a del t aHE2_894* ( 9. 478171220313e - 4) / 2. 20462eS218Ea- 3;
f u n c t i o n c P2( x)
p r o S e c t sHZ, sBZ, 31.2, aH, aB, aD, bH, bB, bD, cH, cE, cf , dH, dB, dK, aH, aB, aD;
y - sHZ' -isH + bHx + cHj:-2 < dHx"3 4 eHx^4) +
sB2-*CaB + bE^x + cE-'x'-Z + dEx' 3 + KB*X~4) +
ED2taI> t bD' x f cD*x'-2 + dl' x~3 + e C x M) ;
r e t u m y ;
e n d f u n c t i o n ;
/ / r h. i s p o r t i o n o f thB :,<>ript i,- d^sxpêrf ^ .r*2c!u2,a(- X^^/R .' slu^
Ea2_over _ Val ue_of _Ea2_c. ver _P_degK;
del t aHEZ_c' . / Br_R de i t a HR2_Bt ui bt t ol e / ( 1. 987*1. 8) ;
Ea3 over _R - BaZ_over _P d6lcaHP2__over_E;
/ / Thz^ pcr t xo. - . ..t t2-. s c r x p t 1^ d:X9ad t o =. , 2^t . 2. , t a tfc^ A2 ^..d i*^ .....2u
/ / tar tii^ ^dytzst^d r a t e ^xpi' ^^-sz' -' "^ ,,^., , , , .
A2 >a A2 Luyban*ep<- Ea2 ova r _Luyban_de, K/ 894. Z S ) / e ^ i - Sa 2_ova r _E/ 894. 26) ;
t l > ' = t 3 : ' u y b a n ^ J S < - Ka 3 : o . . r P _ Lu y b . n _ d a , K/ 8 9 4 . 2 6 ) / e ^ ( - Ha 3 _ o v a r _ P . / 8 9 4 . 2 6 , ;
45
APPENDIX B
ECONOMIC DATA
46
VALUES OF CHEMICAL SPECIES
Table B.l: Toluene and Benzene price
.Material
Toluene
Benzene
Hydrogen
S/gal
0.76
0.80
Specific
gravity
0.866
0.879
information |27, 28|
Water density',
lb/gal
8.33
8.33
S/lb
0.105
0.109
Molecular
Weight
92
78
(95'%) with 5% methane)
S/lbmole
9.66
8.52
1.14
Table B.2: Hydrogen and Methane fuel values information | 1|
Material
fiydrogen
Methane
BTU/lbmole*
1.23E+05
3.83E+05
Current Price, $/10''BTU
4.00
4.00
$/lbmole
0.49
1.53
Diphenyl cost information
.At this point, there is no published price for treating diphenyl as a waste. In order to be
conservative, the price of diphenyl for design is assumed to be $0/lbmole since the
conventional HDA process discharges diphenyl (the b\-product considered to be waste)
and this discharge may bear some cost, where the modified HDA process does not
discharge diphenyl.
47
APPENDIX C
THE CONVENTIONAL DESIGN OF HDA PROCESS
48
REFER TO FIGURE 3.3
Table C l ; Conditions and compositions tor all material streams ofthe conventional HDA process
Fluid Package: Basis-1
Property Package: UNIQUAC - Ideal
Material Stream: H2 Feed
CONDITIONS
Vapor / Phase Fraction
Temperature: (C)
Pressure: (psia)
Molar Flow (Ibmole/hr)
Mass Flow (kg/min)
Vapor Phase
I .()()()()
30.00
500.0
49(1.4
9,(134
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0000
0.9700
0.0000
0.0300
0.0000
Material Stream: Recycle Gas
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
45.00
500.0
3519
276.9
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLi; FRACTKJN
0.0009
0.4329
0.0060
0.5602
0.0000
Material Stream: Sep. bottoms
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
45.00
500.0
454.6
272.0
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.2997
0.0038
0.6403
0.0519
0.0044
Material Stream: Sep. inlet
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Overall
0.8978
45.00
500.0
4446
586.0
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0314
0.3891
0.0708
0.5082
0.0004
Material Stream: Toluene Feed
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
26.98
14.70
273.0
190.2
COMPOSITION
COMPONENTS
Toluene
Tlydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
1.0000
0.0000
0.0000
0.0000
0.0000
49
Table C l continued
Material Stream: I
CONDITIONS
N'apor / Phase FraL'lion
Temperature: (C)
Pressure, (psia)
Molar Flow (Ibmolc'lir)
Mass Flow (kii iiiui)
Material Stream: 4
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid 1
(I 0(100
30.00
50(1.0
273 0
19(1.2
'base
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
Bd^hcnvl
MOLE FRACTION
1OOOO
0.0(100
0 0000
0 0000
0 (1000
Material Stream: 2
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
()\ erall
0.9673
57.56
.500.0
4LV3
371.9
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0306
0 4838
0.0051
0.4805
0,0000
Mat eri al St ream: 3
CONDI TI ONS
Temper at ur e: (C)
Pressure: (psia)
Mol ar Fl ow (Ibmol e/ hr)
Mass Fl ow (kg/ mi n)
Liquid Phase
0.0000
137.8
30. 00
123.5
86.03
COMPOSITION
COMPONENIS
Tol uene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.9995
0.0000
0.0005
0.0000
0. 0000
Mat eri al St ream: 3 (Purge)
CONDI TI ONS
Temper at ur e: (C)
Pressure: (psia)
Mol ar Fl ow (Ibmol e/ hr)
Mass Fl ow (kg/ mi n)
Vapor Phase
1.0000
45. 00
500.0
472. 3
37. 17
C(JMPOSITION
COMPONENTS
Toluene
ll\drogen
Benzene
Methane
BiPhenyl
Liquid Phase
0.0000
140.5
500.0
123.5
86.03
Material Stream: 4 (Methane)
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor I
1.0000
-7.401
480.0
23.06
2.635
'base
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLT; FRACTION
0.0009
0.4329
0.0060
0.5602
0.0000
COMPOSITION
gg COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.9995
0. 0000
0.0005
0.0000
0. 0000
MOLE FRACTION
0.0000
0.0688
0.0005
0.9307
0.0000
50
Ta b l e d continued
Material Stream: 5
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
46.11
505.3
3519
276.9
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0009
0.4329
0.0060
0.5602
0.0000
Material Stream: 5 (Benzene)
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
102.5
30.00
265.5
156.7
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0002
0.0000
0.9997
0.0001
0.0000
Material Stream: 6
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Overall
0.9002
52.62
500.0
4406
562.1
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0907
0.4538
0.0048
0.4507
0.0000
Material Stream: 6 (Diphenyl)
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
196.0
31.00
2.540
2.616
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.2898
0.0000
0.0000
0.0000
0.7102
Material Stream: 7
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.00(10
46.11
505.3
3519
276.9
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0009
0.4330
0.0060
0.5601
0.0000
Material Stream: 8
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
140.5
500.0
123.4
85.98
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.9995
0.0000
0.0005
0.0000
0.0000
51
Table C l continued
Material Stream: 9
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
426.7
500.0
4406
562.1
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0907
0.4538
0.0048
0.4507
0.0000
Material Stream: 10
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
62 1.1
500.0
4406
562.1
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTK3N
0.0907
0.4538
0.0048
0.4507
0.0000
Material Stream: 11
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
666.1
500.0
4406
562.1
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0290
0.3926
0.0657
0.5124
0.0004
Material Stream: 12
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Material Stream: 12 1
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Material Stream: 13
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
45.00
500.0
40 02
23.94
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.2997
0.0038
0.6403
0.0519
0.0044
Liquid Phase
0.0000
45.00
500.0
40.02
23.94
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.2994
0.0038
0.6406
0.0519
0.0044
Vapor Phase
1.0000
648.8
500.0
4446
586.0
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRAC TION
0.0314
0.3891
0.0708
0.5082
0.0004
^^
Table C.I continued
Material Stream: 14
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
290.7
500.0
4446
586.0
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0314
0.3891
0.0708
0.5082
0.0004
Material Stream: 15
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Vapor Phase
1.0000
45.00
500.0
3991
314.1
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0009
0.4329
0.0060
0.5602
0.0000
Material Stream: 16
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
45.00
500.0
414.6
248.0
COMPOSITION
CCJMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.2997
0.0038
0.6403
0.0519
0.0044
Material Stream: 17
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
268.1
480.0
391.5
245.4
COMPOSITION
C()MPONT: NTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.3173
0.0000
0.6780
O.OOOI
0.0046
Material Stream: 18
CONDITIONS
Temperature: (C)
Pressure: (psia)
Mass Flow (kg/min)
Liquid Phase
0.0000
142.4
33.00
126.0
88.64
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.9852
0.0000
0.0005
0.0000
0.0143
53
Table C.2: Parameters for equipment ofthe conventional HDA process
Compressor
Compressor: K-lOO
Duty: 2.4466e-t-05 cal/min
Adiabatic LIT.: 75.00
PolyTropic Eff: 75.00
Furnace
Heater: E-101
Duty: 9.846e-^007 caLmin
Pressure Drop: 0.0000 psi
Cooler
Cooler: E-102
Duty: 1.194e-H008 cal/min
V-100 (Separator)
Vessel Volume: 276.5 ft3
Level SP: 50.00 %
Liquid Volume: 138.2 ft3
Vessel Pressure: 500.0 psia
Duty: 0.0000 cal/min
Heat Transfer Mode: Heatinsj
Pumps
Pump: P-100
Adiabatic Efficiency (%): 75.00
Delta P 485.3 psi
Energy: 2.348e+005 calmin
Pump: P-101
Delta P: 470.0 psi
Energy: L182e+005 cal/min
Heat Exchanger
Heat Exchanger:
PARAMETERS
Exchanger Desig
E-lOO
n (End Point)
Tube Side DeltaP: 0.0000 psi
Shell Side DeltaP: 0.0000 psi
UA: 1.023e-H005 Btu F-hr
Tube Side Data
Heat Transfer Coefficient
Tube Pressure Drop 0.00 psi
Fouling 0.00000 F-hr-ft2/Btu
Tube Length
Tube O.D.
Tube Thickness
Tube Pitch
Orientation
Passes Per Shell
Tubes Per Shell
Layout Angle
TEMA Type
19.69 ft
0.79 in
0.0787 in
1.9685 in
Horizontal
6
156
Triangular (30 degrees)
Passes:
Tolerance: l.OOOOe-04
Shell Side Data
Shell Pressure Drop 0.00 psi
Shell Passes
Shell Series
Shell Parallel
Baffle Type
Baffle CutC'oArea)
Baffle Orientation
Spacing
Diameter
A E L Area
1
10
1
Single
20.00
Horizontal
31 4%l in
28.7430 in
633.03 ft2
54
Table C.2 continued
Plug Flow Reactor
Plug Flow Reactor: PFR-lOO
Physical Parameters
Type : User Specified
T\ pe Direct Q Value
Dimensions
Total Volume: 4066 ttj
Length: 57.00 ft
Diameter: 9.530 ft
Number of Tubes: 1
Void Fraction: 1.0000
Energy Stream : Q Reactor
Heat Transfer: Heating
Duty : 0.0000 cal/min
Wall Thickness:
Void Volume:
1.640e-002 ft
4(166 rt3
Initialize From:
Reaction Info
Reaction Set: Global Rxn Set
Integration Information
Number of Segments: 20 Minimum Step Fraction: l.Oe-06 Minimum Step Length: 5.7e-05 ft
Current
R,\n-1 (Kinetic): Stoichiometry, Basis, Parameters
STOICHIOMETRY
Component Molecular Weight Stoich Coeff
Toluene 92.14 -1
Hydrogen 2.016 -1
Benzene 78.11 1
Methane 16.04 1
Balance Error : 0.0000 Reaction Heat: -1.804c
BASIS
Basis Base Component Rxn Phase
Partial Pres Toluene VapourPhase
PARAMETERS
Forward Reaction Reverse Reaction
A : 3.686e-H006 A' :
E: 9. 157e- 004 E' :
Forward Order
1.000
0.5000
0.0000
0.0000
1004 Btu/lbmole
Reverse ()rder
(1 0000
0.0000
0.0000
0.0000
Min. Temp (C)
-273.1
Max. Temp(C)
3000
Rxn-2 (Kinetic): Stoichiometry, Basis, Parameters
STOICHIOMETRY
Component Molecular Weight Stoich Coeff
Benzene 78.11 -2
BiPhenyl 154.2 1
Hydrogen 2.016 1
Forward Order
2.000
0.0000
0.0000
Balance Error: 0.0000 Reaction Heat: 3490 Btu/lbmole
BASIS
Basis Base Component Rxn Phase
Partial Pres Benzene VapourPhase
PARAMETERS
Forward Reaction Reverse Reaction
A : 0.6272 A' : 0.08124
E : 5.495e-H004 E' : 4.447e+004
Reverse
0.0000
1.000
1.000
Min. Temp (C)
-273.1
Order
Max. Temp (C)
3000
55
Tabl e C.2 cont i nued
Distillation Col umns
Distillation:
Tra\ Summary
Flow Basis:
Reflux Ratio:
Condenser
1 M;iin TS
2 MLiin IS
3 Main TS
4_Ma i n TS
5 Main IS
(1 Mai nTS
7 Mam TS
8 Mai nTS
4 Mai nTS
10 Mai nTS
11 Main IS
12 Mai nTS
13 Main TS
14_Mai n IS
15 Main TS
16 Mai nTS
r Mai nTS
18 Mai nTS
19 Mai nTS
20 Mam TS
2 1 Main TS
22 Mam TS
23 Main TS
24_Mai n TS
25 Main TS
26 Main TS
2: ' _Mai n TS
; Reboiler
Distillation: T-IOI
Tray Summary
Tlou Basis: Molar
T-100
Molar
3.000
Temp.
(C)
102,5
104 0
104 2
104 ^
104 5
104 7
105.0
105,4
105.9
106.8
108.2
110 2
112.9
116.1
119.3
122 2
126 3
130.4
133,9
136.6
138.4
139.6
140 4
140,9
141.2
I4I.5
141.7
141.9
142 4
Reflux Ratio: 0.5000
Condenser
1 Main TS
2 Main TS
3 Mam TS
4 Main TS
5_Mai n TS
6 Main TS
7 Main I S
Reboiler
Temp.
(C)
137 8
137.8
138.1
138.3
138.6
139.2
139.5
143.0
196,0
Pressure
(psia)
30.00
30.00
30.12
30 23
30-35
30 46
30-58
30.69
30,81
30.92
31 04
31.15
31 27
31 38
31.50
31.62
31.73
31.85
31-96
32.08
32 19
32.31
32 42
32.54
32.65
32.77
32.88
33.00
33.00
Pressure
(psia)
30.00
30.00
30.17
30.33
30.50
M) 67
30.83
31.00
31.00
Liquid
(Ibmole/hr)
796.4
801.8
801.8
801.7
801 5
801.0
800.1
798.4
795,4
79(1 4
782.8
772.7
761.3
751.0
742 9
741.3
737 1
735 2
735 4
736 4
737 6
7-i8.6
739.3
739.9
740.3
740.7
741.0
740.3

Liquid
(Ibmole/hr)
61.75
61.56
61 46
61 34
6(1.90
1X4 4
181.7
140.9

Vapor
(Ibmole/hr)

1062
1067
1(167
1067
1067
1066
1066
1064
1061
1056
1(148
1038
1027
1016
1008
615.3
611.0
609 2
609 3
610 4
611.6
612.5
613.3
613.8
614 3
614 6
614 9
614 2
Vapor
(ibmole/hr)

185.3
185.1
1X5.0
1X49
184.4
181,9
179,2
138 4
Feeds
(Ibmole/br)
.
391.5

Feeds
(Ibmole/hr)

126.0

Draws
(Ibmole/hr)
265,5 L
___

-

L

...
...
...
...
...

...

...

126,0 1
Draws
(Ibmole/hr)
123,5 L

...
...
...
L

2.540 L
Duties
(cal/min)
-5.715e+(107
. 3.556e+007
Duties
(cal/min)
-1 076c+(HI7
1.063e+007
56
Table C2 continued
T-102 (Shortcut Column)
PARAMETERS
Component
Light Ke\ Methane
HeavN Ke\ Benzene
Pressures (psia)
Condenser Pressure 480.0
Reboiler Pressure 480.0
RESULTS
Trays / Temperatures
Minimum # of Tra\s
Actual # of Tra\s
Optimal Feed Stage
Condenser Temperature (C)
Reboiler Temperature (C)
Mole Fraction
1 .OOOe-004
5.000e-004
Retlux Ratios
Extemal Retlux Ratio 0.2000
Minimum Retlux Ratio 2.151e-002
Flows
2 546 KcctiT\ Vapor (Ibmole/hr)
6.182 Rectify Liquid (Ibmole/hr)
3.758 Stripping Vapor (Ibmole/hr)
-7.401 Stripping Liquid (Ibmole/hr)
268.1 Condenser Duty (cal/min)
Reboiler Duty (cal/min)
27.68
4.613
27.68
419.2
-6.542e+005
3.025e+007
57
The following is the reactor information in the conventional HDA process.
Inlet
Temperature
Pressure
Molar Flow
Comp Mole Frac (Toluene)
Comp Mole Frac (Hydrogen)
Comp Mole Frac (Beiêne)
Comp Mole Frac (Methane)
Comp Mole Frac (BiPhenyl)
1150
500.0
4383
0,0856
0.4291
0.0053
0.4800
0.0000
F
psia
Ibmole/lir
PFR-100
Pressure Drop
Heat Flow
Reactor Volume
Bed Voldage
0.0000
0.0000
1154
1,0000
kPa
kJ/h
m3
PFR-100
Outlet
Temperature
Pressure
Molar Flow
Comp Mole Frac (Toluenei
Comp Mole Frac (Hydrogen i
Comp Mole Frac (Benzene)
Comp Mole Frac (Methane)
Comp Mole Frac (BiPhenyli
pî
500.0
4383
0.0307
0.3745
0.05%
0.5350
0.0003
F
psia
Ibmole/lir
Outlet
Reactor Q
Reactor Q
Heat Flow 0.0000 kJ/h
10
20 30 40
Reactor length, ft
60
Figure C l : Temperature ofthe reactor in the conventional HDA process
58
8, 00E- 02
? 7. 00E- 02
CO
I 6.00E-02
o
E
5.00E-02
o 4.00E-02
2 3.00E-02
c
2. 00E- 02
o
1.00E-02
O.OOE+00
- +
"Reaction-1
' Reactions-2&3
10 20 30 4 0
Reactor length, ft
50 60
Figure C.2: Reaction rates in the reactor ofthe conventional HDA process
u
ra
o
6.00E-01
5.00E-01
4 .00E-01
3.00E-01
2.00E-01
1 OOE-01
O.OOE-t-00 - ) i <: >>: x * * ? > : * : x ^ > : >K' ^ ^ * ^ ^ ' <* ^ * ^ ^
50
10 20 30 4 0
Reactor Lengt h, ft
60
-Toluene
-m- Hydrogen
~^-- Benzene
-^<Methane
-^te-Diphenyl
Figure C.3: Component mole fraction in the reactor ofthe
conventional HDA process
59
Table C.3: Process unit costs for the conventional HDA process
1
-)
3
4
5
6
7
8
9
10
11
i :
13
14
15
16
1"
18
19
20
Equipment
Feed Pump
Heat Exchanger
Furnace
Reactor(s)
Cooler
Separator
Stabilizer Column
Product Column
Recycle Column
Recycle Pump
Recycle Compressor
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Reboiler
Condenser
Reflux Pump
Label*
P-100
E-lOO
K-101
PFR-lOO
i:-i(i2
v- 100
r-i (i 2
T-IOO
l -IOl
p-101
R-KMl
tor C olumn 1 -100
for Column T-IOO
for Column T-100
for Column 1-102
for Column 1 -I(i2
for Column T-102
for Column 1 -101
for Column 1 -101
for Column 1 -101
Equipment
Cost**
S
%
s
\
$
s
$
$
s
t.
$
$
$
$
$
$
%
$
$
s
s
20.432
167.332
2(1^).451
5 1.49(1
2(1.471
5S.219
35.V20
(i2.0?i)
22.892
17.108
83.585
1(1.1 12
21, 066
9.538
9,980
19.452
9,538
7,329
12.12(1
9.538
869,638
B
$
$
S
s
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
are Module
Cost***
67.(i28
1.14(1.188
791. 724
912. 985
89, 563
419. 924
196,385
216, 767
73, 208
56, 626
22(1.619
53.169
65. 094
31, 570
32,934
82, 087
31. 570
24,185
5 1,1 72
31. 570
4,600,968
* See Flow Diagram for the conventional HDA process (sec Chapter 2)
** - Equi pment Cost - equi pment cost data adjusted for any difference in unit capacil\
and elapsed time since the cost material as generated (usmg cost Index)
*** - Bare Modul e Cost - the sum of t he direct and indirect costs:
Direct Cost:
a. Equi pment f o b . cost
b. Mat eri al s required for installation
c Labor to install equi pment and material
Indirect Cost
a. Freight, msurancc. and taxes
b. Construction o\ erlicad
c. Cont ract or engmceri ng expenses
60
CAPITAL COST ESTIMATION FOR THE CONVENTIONAL HDA PROCESS
(using CAPCOST" (24])
Chemical Engineering Plant Cost Index (CEPCl) = 382
Total Purchase(J Equipment Cost = $ 887,000
Total Bare Module Cost (CS and 0 barg) of Plant = $ 2,753,000
Total Bare Module Cost of Plant = $ 4,554,000
Total Module Cost of Plant = $ 5.373,000
Total Grass Roots Cost of Plant = $ 6.337,000
COMPRESSORS
Compressor, C-101 without drive
Reciprocating Compressor/Blower
Power (kW) = 90
Material of Construction = CS
Number of Spares = 0
Equipment Cost = $ 72 316
Bare Module Cost = $ 209 716
DRIVES
Drive. D-101
Compressor and Blower Drives - Electric - E.xplosion Proof
Power (kW) = 90
Number of Spares =0
Equipment Cost = $11 269
HEAT EXCHANGERS
Heat Exchanger. E-101
Shell and Tube - Fixed Tube Sheet
Area (m2) =2 787.0912
.Material of Construction =SS SS
Tube Side Pressure (barg) =37
Shell Side Pressure (barg) =37
Bare Module Cost = $ 1 146 188
Heat Exchanger, E-102 Kettle Reboiler
Area (m2) =50
Material of Construction =CS CS
Heat Exchanger. E-103 Kettle Reboiler
Area (m2) =20
Material of Construction =CS'CS
Heat Exchanger. E-105 Air Cooled Exchanger
Area (m2) =10
Material of Construction =CS
Heat Exchanger, E-106 Air Cooled Exchanger
Area (m2) =10
Material of Construction CS
Heat Exchanger, E-107 Air Cooled Exchanger
Area (m2) =10
Material of Construction =^CS
Pressure (barg) =1
Pressure (barg) =1
Equipment Cost = $ II 145
Pressure (barg) =1
Bare Module Cost = $28 068
Heat Exchanger, E-108
Area (m2) =50
Material of Construction SS SS
FIRED HEATERS
Heater, H-l01
Non-Reactive Fired Heater
Duty (kW) =984
Tube Pressure (barg) =200 barg
PUMPS
Pump, P-101
Centrifugal Pump
Material of Construction = Cast Iron
Power (kW)= 16.23
Pump. P-102
Centrifugal Pump
Material of Construction
Power (kW) = 2
Cast Iron
Pump, P-I03
Centrifugal Pump
Power (kW) = 2
Tube Material of Construction=
SS
Suction Pressure (barg) = I
Number of Spares = I
Suction Pressure (barg) = 1
EquipmentCost = $9 538
Pump, P-104
Centrifugal Pump
Power(kW) = 2
Equipment Cost = $ 9538
Pump. P-105
Centrifugal Pump
Power (kW) = 2
Cast Iron
EquipmentCost = $9 538
Pump, P-106
Centrifugal Pump
Power (kW) = 2
Pump, P-107
Centrifugal Pump
Power (kW) = 2
Pump. P-108
Centrifugal Pump
Power(kW) = 2
Pump, P-109
Centrifugal Pump
Power (kW) = 2
Bare Module Cost - 5> 3 1 570
EquipmentCost = $ 9 538
62
Pump, P-110
Centrifugal Pump
Material of Construction ^
Power (kW)= 10
Cast Iron
TOWERS
Tower, T-101
Tower Material of Construction= CS
Diameter (m) =1.524
Height/Length (m) =20
Pressure (barg) =1
Tower, T-102
Tower Material of Construction=
Diameter (m) =0.9144
Height/Length (m) =4.27
Pressure (barg) = 1
CS
\ ESSELS
Number of Trays =15
fia\ Material of Construction=
Vessel Cost = $ 58 625
Internals Cost = $0
CS
Number of Trays =7
Tray Material of Construction=
Vessel Cost = $ 10 498
Internals Cost = $ 0
CS
Process Vessel, V-IOI
Material of Construction = SS
Vessel Orientation = Horizontal
Diameter (m) = 2.90
Height/Length (m) = 17.37
Pressure (barg) = 37
Process Vessel, V-102
Material of Construction = SS
Diameter (m) = 0.3
Height/Length (m) = 16.02
Vessel Orientation = Vertical
Diameter (m) = 1.5
Height/Length (m) = 10
Pressure (barg) = 1
Diameter (m) = 2
Diameter (m) = 2
Diameter (m) = 2
Diameter (m) = 2
Height Length (m) = 3
Pressure (barg) = 1
Pressure (barg) = 1
Pressure (barg) = 1
Pressure (barg)= 1
Equipment Cost = $ 19 4.^2
63
Table C.4: Operating cost summary for the conventional HDA process
Electrical power:
K-lOO
P-100
P-101
Fuel (Oil or Gas):
E-101
Cooling water:
E-102
T-100 Condenser
T-101 Condenser
T-102 Condenser
Steam
T-lOORebolier
T-101 Rebolier
T-102Rebolier
BTU/hr
5.K2E+04
5.59E+04
2,8ir-+04
2.34E+07
2.85E+07
1.36E+07
2.56E+06
1.56E+05
8.47F.+06
2.53E+06
1 7.20E+06
Dollars/hr*
0.68
0.65
0.33
93.77
0.53
6.77
1.28
0,08
435.68
130,24
370,62
Total
1,040.63
* based on the utilities prices used by Douglas [1]
64
APPENDIX D
THE MODIFIED DESIGN OF HDA PROCESS
65
REFERTOFICITRFd^
Table D. l: Conditions and compositions for all material streams ofthe modified HDA process
Fluid Package: Basis-1
Property Package: UNIQUAC
Ideal
Material Stream:
CONDITIONS
Benzene Product
Temperature: (F)
Pressure: (psia)
Mass Flow (lb hr)
Liquid Phase
0.0000
165 5
14.70
265.0
2 070c+(104
COMPOSIIION
COMPONI:N IS
I'oluenc
1 lydrogen
Benzene
Methane
UiPhcnyl
Material Stream: Fresh Hydrogen
CONDITIONS
N'apor / Phase Fraction
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
MOLE FRACTION
0.0000
0.0000
0.9997
(1.0002
0.0000
Vapor Phase
1.0000
86.00
500.0
665.4
1622
COMPOSITION
COMPONENTS
Idluenc
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.0000
0 9700
0 OOOO
0.0300
0.0000
Material Stream: Fresh Toluene
CONDITIONS
\' apor / Phase Fraction
Temperature. (F)
Pressure: (psial
Molar Flow (Ibmole'hrl
Mass Flow (Ih'hr)
Material Stream: Fumace
CCJXDITIONS
Temperature: (F)
Pressure, (psia)
Ma.ss Flow (Ib/hr)
Liquid Phase
0.0000
77.0(1
14 70
268.9
2.478e+004
Vapor Phase
1.0000
77,96
14 70
12.93
289.6
COMPOSIIION
COMPONENTS
toluene
1 Kdrogen
Benzene
Methane
BiPhenyl
COMPOSITION
COMPONENTS
1oluene
II\drogcn
Benzene
Methane
liiPhenvl
MOLE FRACTION
1.11000
0.0000
0.0000
0.0000
0.0000
MOLE FRACTION
0.0003
0.0754
0.1191
0 8053
0.0000
.Material Stream: Methane out
CONDITIONS
Temperature: (1 )
Pressure: (psia)
.Molar Flow (Ibmole/hr)
Mass I low (Ib/hr)
Material Stream: To membrane Unit
CONDITIONS
Vapor / Pha.se Fraction
temperature: (F)
Pressure: (psia)
Vlass Flow (Ib/hr)
Vapor Phase
1.0000
166.7
14.70
4 486
318 3
Vapor Phase
1.0000
80.00
496 6
656.5
5418
COMPOSITION
COMPONENTS
Toluene
1 lydrogen
Benzene
Methane
BiPhenvl
COMPOSITION
COMPONENTS
toluene
1 lydrogen
Benzene
Methane
Bil^henyl
MOLE FRACTION
0.0000
0.0008
0.8848
0.1143
O.OOOO
MOLE F RACUON
0 OOOO
0 5720
0. 0038
0. 4242
0 OOOO
66
Tabl e D, 1 cont i nued
Material Stream: I
C(WDIT10NS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Material Stream: 6
CONDHIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Vapor I'liasc
1.0000
710.0
499 5
89.64
826(1
COMPt JSni ON
COMPONENTS
I oluene
I l \ dr ( i ) i ci i
Benzene
Methane
BiPhenvl
Vapor Phase
1 OOOO
1300
498.2
884.8
2 400e+()04
(OMI' OSITION
C(.)MPONENTS
1 <iluene
tlydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
1.0000
0.0000
0.0000
0.0000
0.0000
Material Stream: 2
CONDITIONS
\ apor / Phase Fraction
1 cmperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Material Stream: 3
CONDITIONS
Temperature: (F)
Pressure: (psia)
Molar Flow (Ibmote/hr)
Mass Flow (tb/hr)
Vapor Phase
1.0000
710.0
499.5
89.64
826(1
Vapor Phase
1 OOOO
710. 0
499 5
89. 67
8262
COMPOSI TI ON
COMPONENTS
Tol uene
t l ydr ogen
Benzene
Met hane
Bi Phenyl
COMPOSI TI ON
COMPONENTS
Tol uene
Hydrogen
Benzene
Met hane
Bi Phenvl
MOLL FRACTION
1.0000
O.OOOO
O.OOOO
0. 0000
0. 0000
MOLE FRACTI ON
1.0000
0. 0000
0 OOOO
0, 0000
0 OOOO
Material Stream: 4
CONDITIONS
femperature: (F)
Pressure: (psia)
Molar Flow (Ibmole hr)
Mass Flow (Ib/hr)
\ apor Phase
1 00(10
835 1
499 4
89. 64
8260
COMPOSI TI ON
COMP()Nt -; NTS
l ol uene
Hydrogen
Benzene
Met hane
Bi Phenyl
MOLE FRACTI ON
1.0000
0. 0000
0. 0000
O.OOOO
0. 0000
Vlaterial Stream: 5
CONDITIONS
Temperature: (F)
Pressure: (psia)
.Molar Flow (Ibmole/hr)
.Mass Flow (Ib/hr)
Overall
0 6322
80 00
496 6
1039
3. 767e+004
COMPOSI TI ON
COMPONENIS
Toluene
1 lydriigcn
Ben/ciic
Methane
BiPhenvl
MOLE FRACTI ON
0. 0059
0 3628
0. 3106
0. 2803
0 0404
MOLE FRACTION
0.0004
0.5100
0.2310
0.2306
0.0280
67
Tabl e D. l cont i nued
Material Stream- 7
CCWDITIONS
temperature: (F)
Pressure: (psia)
Molar Flow (tbmole/hr)
Mass Flow (Ib/hr)
Material Stream: 8
CONDITIONS
\' apor / Pha.se Fraction
temperature: (F)
Pressure: (psia)
Molar Flow (Ibmole hr)
Mass Flow (Ib/hr)
Vapor Phase
1.0000
976.6
499 4
89.67
8262
Vapor Pha.se
1.0000
1231
498 2
974 5
3.226e-i-004
COMPOSiriON
COMPONENTS
Toluene
Hydrogen
tienzene
Methane
BiPhenyl
COMPOSITION
COMPONENTS
Toluene
11\ drogcn
Benzene
Methane
BiPhenyl
MOLE l-RACI ION
1.0000
0.0000
0.0000
0 OOOO
0.0000
MOLE FRACTION
0 0924
0 46.^t
0.2097
0-2094
0-0254
Material Stream: 9
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
0.0000
386.2
500-0
40-04
5859
Liquid Phase
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
liiPhenyl
MOLE FRACTION
0 1270
0.0000
0.0001
0.0000
0.8729
Material Stream: 10
CONDITIONS
Temperature: (F)
Pressure' (psia)
Ma,ss Flow (Ib/hr)
Material Stream: 11
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Vlaterial Stream: 12
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (lb hr)
Liquid Phase
0.0000
80.00
496.6
382.0
3.225e+0(14
Liquid Phase
00000
S2 46
500.0
268.9
2.478C+004
Liquid Phase
0 00(10
166,7
14 70
261.1
2.039e+OO4
COMPOSITION
(OMPONLNTS
I (ilucne
I lydrogen
Benzene
Methane
BiPhenyl
COMPOSITION
COMPONt-NTS
Toluene
Hydrogen
Benzene
Methane
BiPhenvl
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
MOLl-; FRACTION
0.0160
0 0031
0.8380
0 0329
0 1099
MOLE FRACTION
1.0000
0.0000
0.0000
0.0000
0,0000
MOLE FRACTION
O.OOOO
0 OOOO
0 9997
0.0002
0.0000
68
Table D.l continued
Material Stream: 13
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (tb/hr)
Material Stream: 14
CONDITIONS
Temperature (F)
Pressure: (psial
Molar Flow (Ibmote'hr)
Mass Flow (tb/hr)
0\ erall
0.9262
392 0
4 99 5
795.1
I 574c K104
COMPOSITION
COMPONI.NIS
Toluene
Hydrogen
Bcn/enc
Methane
BiPhenyl
Vapor 1
1 OOOO
1178
498.5
795 I
1 574e
'base
004
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhen\i
MOLIM-RACIION
0 1191
08118
0.0000
0.0251
0 0440
MOLE FRACTION
0.1191
0.8118
0.0000
0.0251
0(1440
Material Stream 15
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (tb/hr)
0.0000
381.9
14 84
40 04
5859
Liquid Phase
COMPOSIIION
COMPONENIS
1 oluciic
Hydrogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0.1270
0.0000
0.0001
0.0000
0.8729
Material Stream: 16
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Material Stream: 17
CONDITIONS
Temperature: (F)
Pressure:(psia)
Mass Flow (Ib'hr)
Material Stream 18
CCJND1T10NS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib/hr)
Vapor Phase
1-0000
1300
498 4
795 2
1 574c*0(14
Vapor Phase
t-00(10
1300
498-1
974.5
3.226e+004
Liquid Phase
0.0000
386.2
500.0
40.05
5860
COMPOSITION
COMPONENTS
Toluene
1 lydrogen
tênzene
Methane
BiPhenyl
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenvl
COMPOSITION
COMlÔNENTS
Toluene
H>drogen
Benzene
Methane
BiPhenyl
MOLE FRACTION
0 0276
0.7060
0.120(1
0.1167
0 0298
MOLE FRACTION
0.0052
0.3864
0.2760
0.2965
0.0359
MOLE FRACTION
0.1271
0 0000
0.0001
0.0000
0.8728
69
Table D.l continued
Material Stream: 19
CONDITIONS
Temperature: (F)
Pressure:(psia)
Molar Flow (tbmote.'hr)
Mass Flow (tb/hr)
Material Stream: 20
CONDITIONS
V apor / Phase Fraction
Temperature: (F)
Pressure: (psia)
Molar How (Ibmole hr)
Mass Flow (lb,hr)
Material Stream: 21
CCWDITIC^NS
V apor / Phase Fraction
Temperature: (F)
Pressure (psia)
Molar Flow (Ibmolehr)
Mass Flow (tb/hr)
Material Stream, 22
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (Ib hr)
Vapor Phase
1.0000
1176
49S4
884.8
2.40()e+()04
Overall
0 0388
77.85
14 84
318.0
2.684e+004
0\ erall
0.8326
344 1
497 1
1039
3.767e+0(14
Vapor Phase
1 OOOO
1130
499 0
795.1
1 574c^004
COMPOSI TI ON
COMPONENTS
Toluene
t l ydrogen
Benzene
Met hane
Bi Phenyl
COMPOSITICJN
COMPONENTS
Tol uene
Hydrogen
Benzene
Met hane
Bi Phenyl
COMPOSI TI ON
COMPONENTS
Toluene
1lydrogen
Benzene
Met hane
Bi Phenyl
COMPOSI TI ON
COMPONENTS
Toluene
1 l ydrogen
Benzene
Met hane
Bi Phenyl
MOLE FRACTI ON
0.1261
0 6345
0, 1078
0 1049
0, 0267
MOLE FRACTI ON
0.016(1
0.0031
0. 8380
0. 0329
0. 1099
MOLE FRAC TION
0 0059
0. 3628
0. 3106
0. 2803
0. 0404
MOLE FRACTI ON
0. 1191
0. 8118
0. 0000
0. 0251
0 0440
Mat er i al St r eam: 23
CONDI TI ONS
Vapor / Phase Fract i on
Temperamre: (F)
Pressure: (psia)
Vlass Flow (tb/hr)
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (tb/hr)
Liquid Phase
0 0000
80.00
14.70
3.899
304 1
Overall
0.1309
80 00
14.70
4 486
318.3
COMPOSI 1 ION
COMPONENTS
Toluene
t1>clrogen
Benzene
Methane
BiPhenvl
COMPOSITION
COMPONENTS
1 oluene
Hydrogen
lienzene
Methane
BiPhenyl
MOLE FRACTION
0.0000
0.0000
0.9982
0.0018
0.0000
MOLE FRACTION
0.0000
0.0008
0,8848
0.1143
0,0000
70
Tabl e D. l cont i nued
Material Stream: 25
CONDITIONS
Vapor / Pha.se Fraction
Temperature: (F)
Pressure (psia)
MiLss Flow (Ib/hr)
\ apor Phase
1.0000
1 148
49S 1
1039
3.767e+004
COMPOSIIION
COMPONENTS
loluene
Hydrogen
Benzene
Methane
BiPhenyl
Material Stream: 26
CONDITIONS
Vapor ' Phase Fraction
Temperature: (F)
Pressure: (psia)
Liquid Phase
0,0000
77.85
14 84
COMPOSITION
COMPONENTS
Toluene
tlydrogen
MOLE FRAC HON
0.0059
0.3628
0.3106
0 2803
0.0404
MOLE FRAC t30N
0.0167 i
0.0000 I
Pressure: (psia)
Molar Flow (Ibmolehr)
NLissFlow (t hhr)
14 84
305.6
2.657c + (l(14
Benzene
Methane
BiPhenyl
0.8671
0.0019
0.1144
Material Stream: 27
CONDITIONS
Temperature: (F)
Pressure:(psia)
Mass Flow (tb/hr)
Vapor Phase
1.0000
80.00
14.70
0.5872
14.18
COMPOSITION
COMPONENTS
Toluene
ll\drogen
Benzene
Methane
BiPhenvl
MOLE FRACTION
0.0000
0.0063
0.1321
0.8616
0.0000
Material Stream: 28
CONDITIONS
Temperature: (F)
Pressure: (psia)
Mass Flow (tb/hr)
CONDITIONS
Temperature: (F)
Pressure: (psia)
Viotar Flow (Ibmole/hr)
Mass Flow (Ib/hr)
CONDITIONS
Vapor Phase Fraction
temperature (Fl
Pressure: (psia)
Vlotar Flow (tbmole/hr)
V-lass Flow (Ib/hr)
Vapor Phase
1.0000
77.85
14,84
12,34
275,4
Vapor Phase
1,0000
749 7
497,6
1039
3.767C+004
Liquid Phase
0.0000
80 04
500,0
382.0
3 225e + (l04
COMPOS1TKW
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenyl
COMPOSITION
COMPONENTS
Toluene
Hydrogen
Benzene
Methane
BiPhenvl
CO VI POSITION
COMPONENIS
Toluene
11\ drogcn
Benzene
Methane
BiPhenvl
MOLE FRACTION
0,0003
0.0786
0.1185
0 8026
0.0000
MOLE FRACTION
0.0059
0.3628
0.3106
0.2803
0.0404
MOLE FRACTION
0.0160
0.0031
0.8380
0.0329
0.1099
71
Table D.l continued
Matcn.il Stream 31
CONDITIONS
Temperature: (F)
Pressure: (psia)
Molar I'low (tbmole/hr)
Mass Flow (Ib/hr)
Vapor Phase
1.0000
7100
499 5
268.9
2 478e*004
COMPOSIIION
COMlÔNI'NTS
Toluene
Hydrogen
Benzene
Methane
BiPhenvl
MOLE FRACTION
1 000(1
O.OOOO
0. 0000
0. 0000
0 0000
Material Stream: 32
CONDITIONS
N'apor / Phase Traction
Temperature: (F)
Pressure: (psia)
1 Mass Flow (tb/hr)
Material Stream: 34
CONDITIONS
Temperature: (F)
Pressure;(psia)
Mass Flow (tb/hr)
Material Stream: 36
CONDITIONS
\ a p o r / Phase Fraction
1 Temperature: (F)
i Pressure: (psia)
Mass Flow (tb/hr)
Liquid Phase
0.0000
SO 04
50(1 0
3 1 S 0
2.(iS4c>004
Liquid Phase
0.0000
80.04
500 0
64.00
5403
Liquid Phase
0 000(1
80 04
500.0
64 00
5403
COMPOSITION
COMPONENl S
Toluene
1 lydrogen
Benzene
Methane
BiPhcn\l
COMPOSITION
COMPONENTS
Toluene
1 lydrogen
Benzene
Methane
BiPhenyl
COMPOSITION
COMPONENTS
Toluene
11> drogcn
Benzene
Methane
BiPhenyl
MOLE FRAC HON
0. 0160
0 0031
0 8-^SO
0.(1329
0 1099
MOLE FRACTI ON
0. 0160
0. 0031
0. 8380
0. 0329
0. 1099
MOLE I-RACTION
0 0160
0 0031
0. 8380
0. 0329
0. 1099
72
Tabl e D. 2: Paramet ers for equi pmem of t he modi t i ed HDA
Separat ors
process
Separator: V-tOO
N'essel Volume: 185.2 ft3
1 cvcl SP: 50.00 "n
Liquid Volume: 92.60 rt3
Separator- V-101
Vessel Volume: 4.320 rt3
l.e\el SP: 50.00 "o
Liquid Volume: 2.160 tt3
Vessel Pressure' 496.6 psia
Pressure Drop: 0 OOOO psi
t)ut> 0.0000 Btu/hr
Heat Transfer Mode: Fleating
Separator: V-102
\ essel Volume: 116.6 1^3
Le\el SP' 50.00 "o
Liquid \ olume: 58 32 03
Vessel Pressure 14 70 psia
Duty: 0.0000 Btu/hr
Heat Transfer Mode: Heating
Vessel Pressure: 14.84 psia
Duty: 0.0000 Btu/hr
Heat TransTer Mode. Heating
Heat Exchanger s
Heat Exchanger: E
Exchanger Design
Tube Side DeltaP:
Shell Side DeltaP:
- t oo
(End Point)
0.5000 psi
0.5000 psi 1
CA l.080e+005 Btu/F-hr
Tolerance: 1 OOOOi
Tube Side Data
'-04
Tube Pressure Drop0.50 psi
Fouling 0.00000 F-hr-t't2/Btu
Tube Length
Tube O.D.
Tube Thickness
Tube Pitch
Orientation
Passes Per Shell
1 ubes Per Shell
Layout Angle
TEMA Type
19.69 ft
0.79 in
0-0787 in
1 9685 in
Horizontal
2
160
A E L
asses ---
Shell Side Data
Heat TransTer Coefficient
Shell Pressure Drop0.50 psi
Fouling 0.00000 !-hr-ft2/Btu
Shell Passes 1
Shell Series 5
Shell Parallel 1
Battle 1 \pe Siimle
liaftleCulC'i.Aica) 20.00
BaTtle (Jrientation Honzontal
Spacing 31 49(il m
Diameter 29 (1964 in
.Area (i49 26 Tt2
Heat Exchanger: I
Exchanger Design
Tube Side DeltaP:
Shell Side DeltaP:
-105
(End Point)
0.5000 psi
0.5000 psi
UA: 1.2096-1-005 Btu/F-hr
Tolerance: 1.0000
Tube Side Data
>(14
Heat transfer Coefficient
Tube Pressure Drop0.50 psi
Tube Length
tube O.D.
Tube Thickness
Tube Pitch
Orientation
Passes Per Shell
Tubes Per Shell
Layout Angle
TEMA Type
19 69 ft
0 79 in
0.0787 in
1 9685 in
Horizontal
2
160
A E L
Passes:
Shell Side Data
Heat Transfer Coet'tlcient
Shell Pressure Drop0.5(l psi
l-outing 0 00000 F-hr-ft2/Btu
Shell Passes 1
Shell Series 4
Shell târallel 1
Baffle Type Single
Baffle CutC'oArea) 20.00
liaffle (Jrientation Horizontal
Spacing 31.4961 in
Diameter 29.0964 in
Area 649 26 rt2
73
Tabl e D.2 cont i nued
Pl uo Fl ow React ors
Plug Flow Reactor: PFR-lOO
T.\ pe User Specified
Heat Transfer : Heating
T\ pe : Direct Q Value
Duty . 0.0000 Btu/hr
Plug Flow Reactor: PFR-101
Physical Parameters
T\ pe : User Specified
T\pe : Direct Q Value
I)ut> : 0.0000 Btu/hr
Total Volume: 311.0ft3
Length: 229.9 ft
Diameter: 1.312 ft
Number of Tubes: 1
Wall Thickness: L640e-0(J2 ft
Total Volume: 1159 ft3
Length: 857.(1 ft
Diameter: 1.312 ft
Number of'Tubes: 1
Wall Thickness: 1.640e-002 ft
Plug Flow Reactor: PFR-102
Physical Parameters
Type : User Specified
T\pe : Direct Q Value
Duty : 0.0000 Bfti/hr
Total Volume: 622.0 ft3
Length: 459.9 ft
Diameter: 1.312 ft
Number of Tubes: 1
Wall Thickness: 1 64(le-0()2 ft
Distillations
Distillation: T-100
Tra\ Summary
Flow Basis: Molar
Reflux Ratio: 2.500
Condenser
l ^ Vl a i nTS
2 _ Ma i n TS
. i^Vlain TS
4 _ Ma i n TS
5_Mai n TS
6 Main TS
^^Vl a i nTS
8_Vl ai n TS
9 _VIain TS
l O^VI ai nTS
1 l _ Ma i n TS
12_Ma i nTS
13__MainTS
14_Ma i nTS
15_Mai n IS
16_Mai n TS
17__Main TS
18 Main TS
19 Main TS
20 Main TS
Reboiler
Temp.
(F)
166.7
Pressure
(psia)
14.70
Liquid Vapor
(Ibmole/hr) (Ibmole/hr)
664.0
173.7
173.7
173.8
173.8
173.9
174 .0
174 2
174 5
175.1
177 2
182.9
193.2
206.5
218.2
226.0
230,3
232.3
233.3
234 .0
24 8.3
381.9
14 .70
14 70
1 4 71
14 72
14 73
14 73
14 74
14 75
14 .76
14 .77
14 .77
14 .78
14 .79
14 .80
14 80
14 .81
14 .82
14 83
14 .84
14 X4
14 84
676 2
676 2
676.1
676.1
675 9
675.6
675 1
674 .0
669 9
104 7
1027
1005
991.3
988.2
990.(1
992.0
993 3
993.4
962.8
680.2

929.6
941.8
941.8
941.7
941.7
941 5
941 2
940,7
939.5
935 5
1007
987.1
965.1
951.3
948,2
949,9
952 0
953 2
953,3
922,8
64(1 2
Feeds
(Ibmole/hr)

Draws
(Ibmole/hr)
4.486 V
261.1 L
Duties
(Btu/hr)
-1.248e+007
305.6
40 04 1.413e-i-007
74
Tabl e D.2 cont i nued
Heat ers
Heater: E-101
Duty: 5 713e+005 Btu/hr
Heater: E-102
Duty: 1.260e-i-006 Btu/hr
Heater: Fumace
Duty: 6.620e-F005 Btu/hr
Cool er s
Cooler: E-103
Dut\-: 7.700e+006 Btu/hr
Cooler: E-104
Dutv 6,394e+0(l4 Btu/hr
Pressure Drop (1 1000 psi
Pressure Drop: 0.0000 ps
Recycle RCV-1
NCMI.RICAL
Adj ust s
Adjust: ADJ-Tin2
Solving Parameters
Adjust: ADJ-Tin3
Solving Parameters
Adjust: ADJ-TinI
Solving Parameters
Pumps
Pump: P-100
Delta P: 485 2 psi
Energy: 1.290e+(l()4 Btu/hr
Pump: P-101
Adiabatic Efficiency ("o): 75.00
Delta P: 485 3 psi
IJiergy: 5.5OOc+004 Btu/hr
Pump: P-102
.Adiabatic Efficiency (%) 75.00
Delta P: 3 40(1 psi
Energy: 484.6 Btu/hr
Recycl es
Recycle: RCY-T and D
Nl^MFRICAI.
Acceleration l>pe: Wegstein
Iteration Tvpe Simultaneous
Acceleration T>pe: Wegstein
Iteration Type: Nested
Source Tor Target Value User Supplied
Target Value: 1300 F
Source for Target Value: User Supplied
Source for Target Value: User Supplied
75
The following is the reactor Section 1 information in the modified HDA process.
0)
3
->
ra
a>
Q.
E
0)
1320
1300
1280
1260
1240
1220
1200
1180
1160
50 100 150
Reactor length, ft
200 250
Figure D. 1: Temperature profile of Reactor 1 in the modified HDA process
SI
I
e
/
f
t
3
-
F
1

R
a
t
e
,

I
b

R
e
a
c
t
i
o
r

3.OOE-01
2.50E-01
2.00E-01
1.50E-01
1.OOE-01
5.00E-02
O.OOE+00
-5.00E-02
-1.00E-01
Reaction-1
Reactions-2&3
50
100 150
Reactor l ength, ft
200 250
Figure D.2: Reaction rates in Reactor 1 ofthe modified HDA process
76
9.OOE-01
8.OOE-01
7.OOE-01
6.OOE-01
c
o
g 5.OOE-01
ra
u.
o> 4 .OOE-01
o
3.OOE-01
-
'~~^-
""*--_
50 100 150
Reactor Lengt h, ft
200 250
-Tol uene
- Hydrogen
-5r- Benzene
->^-Methane
- * - Di phenyl
Figure D.3: Component mole fraction in Reactor 1 ofthe modified HDA process
77
1320
1300
u. 1280
o
^ 1260
re
g. 1240
E
- 1220
1200
1180
- - r-
^^
' h -
1
- - - . J .
1
j
!
1
1
1
100 200 300 400 500 600
Reactor length, ft
700 800 900
Figure D.4: Temperature profile of Reactor 2 in the modified HDA process
-
h
r

CO
/
f
t

o
l
e

E
.o
o
*.
ra
CH
c
o
'*>
u
0)
a:
2.50E-01
2.OOE-01
1.50E-01
1.OOE-01
5.00E-02
O.OOE+00
-5.00E-02
Reaction-1
Reactions-2&3
200
400 600 800
Reactor length, ft
1000
Figure D.5: Reaction rates in Reactor 2 ofthe modified HDA process
78
6.00E-t-02
500E+02
c
o
o
re
0)
O
4 .00E-I-02
3.00E+02
2.00E-t-02
1,00E-t-02
O.OOE-^00
c.:.X-X-**-XHXXXX
-Toluene
-m Hydrogen
-& Benzene
-^^Methane
-^KDiphenyl
0 200 4 00 600 800 1000
Reactor Length, ft
Figure D.6: Component mole fracfion in Reactor 2 ofthe modified HDA process
79
1310
1300
1290
L l .
o 1280
3
1270
0}
E 1260
a>
1250
1240
1230
Jf
D 100
. . 4 . . . . . . :
jAr^
-- . :
---'- i-
200 300
Reactor length. ft
- -
'
400
-
500
Figure D.7: Temperature profile of Reactor 3 in the modified HDA process
k .
s.

V
o
E
a
<S
* j
CC
c
o
+J
o
ro
CC
2.50E-01
2.OOE-01
1.50E-01
1.OOE-01
500E-02
O.OOE+00
Reaction-1
Reactions-2&3
100 200 300
Reactor length, ft
^^S^^^*if4waB^
400
500
Figure D.8: Reacfion rates in Reactor 3 ofthe modified HDA process
80
c
i
c
t
i
o

u.
0)
M
o

5.00E+02
4,50E+02
4.00E+02
3.50E-I-02
3.00E-t-02
2.50E+02
2.00E+02
1.50E+02
1.00E+02
5.00E+01
O.OOE+00
S-H-a-HIHl -B
x-)<-^^-x
^ - ^ - -Jk-TftrA*r~AA,
100 200 300
Reactor Length, ft
400 500
-Toluene
- Hydrogen
-?: Benzene
-^<Methane
-*-Di phenyl
Figure D.9: Component mole fraction in Reactor 3 ofthe modified HDA process
81
Table D,3: Process unit costs for the modified HDA process
1
-
1
4
5
6
7
8
9
10
11
i :
1.3
14
i,>
16
17
18
Equipment
Feed Pump
Heat Exchanger
Furnace
Reactors
Cooler
Separator
Product Column
Recycle Pump
Separator
Separator
Heat Exchanger
Heat Exchanger
Heater
Heater
Cooler
Reboiler
Condenser
Reflux Pump
Label*
P-101
L-lOO
Furnace
PFR-lOO, PFR-101,
PFR-102
E-103
\ - 100
T-IOO
P-100
V-102
V-IOI
E-IO.S
E-106
E-101
E-102
K-l(14
for Product t olumn T-
100
for Product Column T-
100
for Product C olumn T-
100
Equipment
Cost**
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
20,432
41,833
109,961
195,000
37,584
16,931
31,542
11,920
12,129
2,300
13,152
8,860
Bare Module
Cost***
$
$
$
S
$
$
s
$
$
$
$
s
Included in
Included in
16,843
16,112
21,066
9,538
$
s
$
s
67,628
286,547
415,655
220,000
130,915
95.623
133,107
30,454
37,479
7,107
45.811
30,861
Furnace
Furnace
55,581
53,169
65,094
31,570
565,203 $ 1,715,601
* - See Flow Diagram for the modified HDA process (see Chapter 3)
** - Equipment Co.st - equipment cost data adjusted for any ditTerence in unit capacity
and elapsed time since the cost material was generated (using cost index).
*** - Bare Module Cost - the sum ofthe direct and indirect costs:
Direct Cost:
a. Equipment f o.b. cost
b. Materials required for installation
c. Labor to install equipment and material
Indirect Cost:
a. Freight, insurance, and taxes
b. Construction overhead
c. Contractor engineering expenses
82
CAPITAL COST ESTIMATION FOR THE MODIFIED HDA PROCESS
(using CAPCOSr [24])
Chemical Hngineering Plant Cost Index (CEPCl)
Total Purchased Equipment Cost = $ 623,000
Total Bare Module Cost (CS and 0 barg) of Plant
Total Bare Module Cost of Plant = $ 1,906,000
Total Module Cost of Plant = $ 2.249,000
Total Grass Roots Cost of Plant = $ 2.733,000
= ^Ri
= $ 1.381,000
HEAT EXCHANGERS
Heat Exchanger, E-101
Area (m2) =696.7728
Material of Construction =SS SS
Heat E.xchanger, E-102
Kettle Reboiler Area (m2) =50
Material of Construction =CS'CS
FIRED HEATERS
Heater. H-l01
Non-Reactive Fired Heater
Duty (kWj =984
Tube Pressure (barg) =200 barg
PUMPS
Pump, P-IOI
Centrifugal Pump
Material of Construction =
Iron Power (kW)= 16.23
Cast
Equipment Cost = $41,833
Bare Module Cost = $ 286,547
Equipment Cost = $ 16,112
Tube Material of Construction=SS
Equipment Cost = $ 20.432
Pump, P-102
Centrifugal Pump
Power (kW) = 3,81
Cast Iron
Equipment Cost = $ 1 1,920
Pump, P-103
Centrifugal Pump
Power (kW) = 0.75
Pump, P-104
Centrifugal Pump
Power (kW) = 2
Bare Module Cost = $31,570
83
TOWERS
lower, T-101
Tower Material of Construction= CS
Diameter (m) =1.5
Height/Length (m) =10
Pressure (barg) =1,5
Number of Trays =20
Tray Material of Construction= CS
Vessel Cost = $31,542
Internals Cost = $ 0
VESSELS
Diameter (m) = 2.5
Diameter (m) = 2
Height/Length (in) = 4
Pressure (barg) = 1
Diameter (m) = 0.6
Pressure (barg) = 1
Diameter (m) = 2
Height Length (m)= 10
Pressure (barg) = 1
REACTOR
USER ADDED EQUIPMENT
User Added Equipment - 10 in Pipe
Bare Module Factor (CS -*- 0 barg)=
Bare Module Factor (actual)= 1.12
Purchased Equipment Cost = $ 195,000
Table D.4: Operating cost summary for the moditied HDA process
Electrical power:
P-100
P-101
P-102
Fuel (Oil or Gas):
E-101
E-102
Furnace
Cooling water:
E-103 ^
E-104
T-UlO Condenser
Steam
T-100 Rebolier
BTU/hr
1.29E-^04
5,50E-H04
4.85E-H02
5.7IE-^05
l,26E+06
6.62E-^05
7.70E+06
6.39E-^04
1.25E-H07
I.4IE+07
Dollars/hr*
0.15
0.64
0,01
2.29
5.04
2.65
0.04
0.04
6.77
242.36
Total 259,98
* based on the utilities prices used by Douglas [1
85
PERMISSION TO COPY
In presentmg this thesis m partial fulfillment ofthe requuements for a masters
degree at Texas Tech University or Texas Tech University Health Sciences Center, I
agree that the Library and my major department shaU make it fiêely avaUable for
research purposes. Permission to copy this thesis for scholarly purposes may be
granted by the Duector ofthe Library or my major professor. It is understood that
any copymg or publication of this thesis for financial gain shaU not be aUowed
without my ftirther wntten permission and that any user may be liable for copyright
mftingement.
Agree (Permission is granted.)
Student Signature Date
Disagree (Permission is not granted.)
Student Signature Date

Example of HDA

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Example of HDA

Enviado por

Direitos autorais:

Formatos disponíveis

AN EXAMINATION OF MODIFIED HIERARCHICAL DESIGN

STRUCTURE FOR CHEMICAL PROCESSES

Você também pode gostar