HDA Process PDF

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
Vll
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
Mil
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 carbon steel
D diphenyl
H hN'droiicn
HDA the hydrodealkylation of toluene to benzene
M methane
P pressure
PFR plug-flow reactor
SS stainless steel
TL 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.
1 Constraints on the reactor temperature.
J. 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.

Table 2.1: Comparison of textbook examples using the HDA process
Textbook Number of Number of Discharge of Recycle of

.Author chemical distillation diphenyl as a diphenyl to the
reactions columns pollutant reactor
considered
Douglas |1] 1 -> Considered Considered
1 urton et al. [6] 1 1 Not considered Not considered
Smith [11] 1 C onsidered Not considered
Siederetal. |2] T .1 Considered Not considered
Luyben et al. [3] 1
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
5°o 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: 2C„H„ ^ 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) = X s , 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 Dimensionless reaction velocity constant, k^v
644.26 0.15
699.82 1.00
755.37 5.00
810.93 ' 20.00
866.48 70.00
922.04 200.00
977.59 500.00
1,033.15 1,000.00
constants at different temperatures are plotted using the Arrhenius equation.
La, (2-6)
ln(k,A') = -I- constant
RT
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,,^

(2-9)
R R R
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 ' Ea,/R

= 5.987-lO'e.xpl (2-
894.26 894.26
For Reaction 3.
/\ f Ea,/R^
•M„d,„MC,l,eXP 2.553 lO'exp (2-12)
894.26 894.26
Soix ing these expressions, the following xalues arc obtained (see Appendix A):
Ibmole
A:,, „„ =0.62717-
min - It - psia"
Ibmole
A,„d,„s,ed,-0.08124-
min-ft' -psia"
Using these calculated x alues. the adjusted reaction rate expressions are:
( 2.5616-10'^
r, = 3.6858-lO'exp PTPH (2-131
T
1.5362-10 4 X
r, =0.62717 exp Pn" (2-14)
T
^ 1.2237-10"'^
r, =0.08124 exp PD PI (2-15)
T
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
Recycle of H and M (gas-phase)
H ^ H
M ^r
M
Reactor Separator
Tl System System
i k ^ n
Recycle af TL (liquid-phase)
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
Fresh Fresh Reactor Reactor By-

Product Gas Toluene
Purge Product
Toluene Hydrogen Inlet Effluent Stream Recycle Recycle
Stream Stream
Stream Stream Stream Stream (Benzene) Stream Stream
(Diphenyl)
Flow rate,
285.9 4%.4 4 382.5 4 382 5 636.8 265 6.8 3 519.2 82.1
Ibmole hr
Temperature, "F 86 86 1 150 1 263 115 211 559 115 272
Mole fraction
H 0.0000 0.9700 0.42') 1 0.3644 0 391)2 0.0000 0.0000 0.3992 0.0000
M 0.0000 0.0300 0.4800 0.5463 0.5937 0.0000 0.0000 0.5937 0.0000
B 0.0000 0.0000 0.0053 0.0685 0.0065 0.9997 0.0000 0.0065 0.0006
TL 1.0000 (1 0000 0.0856 0.01^)3 0.0006 0.0003 0.0003 0.0006 0.9994
D 0.0000 0.0000 0.0000 0.0015 0.0000 0.0000 0.9997 0.0000 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
HDA Process ->• Benzene
Hydrogen
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

cost
(compressor) and reducing the operating cost ofthe process.
II ^ H
M
M
i Reactor Separator ^ rt
Tl System System
i
Recxcle of TL and D (liquid-phase)
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 _
TL,n/n TL,„/n TL,„/n
Hjn Section Section 2 Section n

n=l n=2
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

Vn
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-\\
TL,„
H„ V n j
>5 (3-2)
TL„ TL„
n
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 13 15
n (number of reactor sections)
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
X
-a
-5
OJ
3
OB
24
Table 3.1: Kex process streams for the modified HDA process
Total
Fresh Fresh Reactor Product Toluene and
Reactor Purge
Toluene Hydrogen Effluent Stream Diphenyl Recycle
System Stream
Stream Stream Stream (Benzene) Stream
inlet
Flow rate,
269 665.6 976.8 976.^) 656.3 265.1 42.2
Ibmole/hr
Temperature, "F 86 86 1175 1300 80 167 1168
Mole fi-action
H 0.0000 0.9700 0.6609 0.3856 0.5723 0.0000 0.0000
M 0.0000 0.0300 0 0204 0.2')5S 0 4240 0.0002 0.0000
B 0.0000 0.0000 0.0000 0.2753 0.0037 0.^)')^)7 0.0001
TL 1.0000 0.0000 0.2853 0.0100 0.0000 0.0001 0 2293
D 0.0000 0.0000 (1.0333 0.0333 0.0000 0.0000 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
Product Product Reactant 1 Reactant "i
all products
flow rate, value, z
all law inalenais
flow rate,
Ibmole/lir
value,
$/lbmole^
(4-
Ibmole/hr $/lbmole
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.
BenzeneV < Purge

^ Value of ^ ^ Value of ^
Production Floxv
EP = Benzene, + Purge,
Rate, Rate,
$/lbmole $/lbmole
Ibmole/hr V Ibmole/hr
^Diphenyl ^ (4-2)
^Toluene ^ '^ Hydrogen y Value of ^
^ Value of ^ ^ Value of ^
Flow Feed Feed Hydrogen
Diphenyl, Toluene,
Rate, Rate, Rate, Feed,
$/lbmole J $/lbmole
Ibmole/hr, Ibmole/hr / Ibmole/hr ) \ $/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 Modified Design Conventional Design

1 Heat exchanger $41,833 $ 167,332
2 Furnace $ 109,961 $209,451
">Reactor sx stem $ 195,000 $ 51.490
4 Separation sx stem $ 164,045 $ 320.240
5 Recycle coinpressor N/A $ 83,585
Total $ 510,839 $ 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
Eciuipment Modified Design (-'onventional Design

1 Heat exchanger $ 286,547 $ 1,146.188
"> Furnace $415,655 $791,724
3 Reactor sx stem $ 220,000 $912,985
4 Separation system $ 609,645 $ 1,399,198
5 Recycle compressor N/A $226,619
Total S 1,531,847 $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
Modified Design Conventional Design
Equipment Label (Figure 3.6) Cost Label (Figure 2.3) Cost
1 1-êed Pump P-101 $ 20.432 P-100 $ 20,432

2 -leat Exchanger E-lOO $41,833 E-lOO $ 167.332
3 -•urn ace Furnace $ 109,961 E-101 $ 209,45 1
PFR-100, PFR-101,
4 Reactor(s) PFR-102 $ 195,000 PFR-lOO $51,490
5 Cooler E-103 $37,584 E-102 $26,471
6 Separator V-100 $ 16,931 V-lOO $58,219
7 Stabilizer Column N/A N/A T-102 $35,920
8 iProduct Column T-1 GO $31,542 T-100 $62,059
9 Recxcle Column N/A N/A r-101 $ 22.892
10 IRecxcle Pump P-100 $ 11.920 P-lOl $ 17,108
11 Recycle Compressor N/A N/A K-lOO $83,585
12 Separator V-102 $ 12.129 N/A N/A
13 Separator V-101 $ 2,300 N/A N/A
14 Heat Exchanger E-105 $ 13,152 N/A N/A
15 Heat Exchanger E-106 $ 8,860 N/A N/A
Included in N/A N/A
16 Heater E-101 Furnace
Included in N/A N/A
E-104 $ 16,843 N/A N/A
18 Cooler
For Column T-100 $ 16,112 For Column T-100 $ 16,112
19 Reboiler
For Column T-100 $21,066 For Column T-100 $21,066
20 Condenser
21 Reflux Pump
N/A N/A For Column T-102 $ 9,980
22 Reboiler
23 Condenser
N/A N/A For Column T-102 $9,538
24 Reflux Pump
25 Reboiler
26 Condenser
N/A N/A lor Column T-101 $9,538
27 Reflux Pump
$ 565,203 S 869,638
Total
31
Table 4.4: Bare module costs ofthe HDA process

Equipment Label (Figure 3.6) Cost Label (Figure 2.3) Cost
1 1êed Pump P-101 $ 67,628 P-100 $ 67,628
2 -leat Exchanger E-lOO $286,547 E-lOO $ 1,146,188
3 "urnace Furnace $415,655 E-101 $791,724
PFR-lOO, PFR-101,
4 êactor(s) $ 220.000 PFR-lOO $912,985
PFR-102
5 Cooler E-103 $ 130.915 L-102 $ 89,563
6 Separator V-lOO $ 95,623 V-lOO $419,924
7 Stabilizer Column N/A N/A T-102 $ 196,385
8 Product Column T-100 $ 133,107 T-100 $216,767
9 Recycle Column N/A N/A T-101 $ 73,208
10 Recycle Pump P-lOO $ 39,454 P-101 $ 56,626
11 Recycle Compressor N/A N/A K-lOO $226,619
12 Separator V-102 $ 37,479 N/A N/A
13 Separator V-lOl $7,107 N/A N/A
14 Heat Exchanger E-105 $45,811 N/A N/A
15 Heat Exchanger 1-.-106 $30,861 N/A N/A
Included in N/A N/A
Included in N/A
17 Heater E-102 N/A
Furnace
E-104 $55,581 N/A N/A
18 Cooler
19 Reboiler
For Column T-100 $ 65,094 For Column 1-100 $ 65,094
20 Condenser
21 Reflux Pump
-n Reboiler N/A N/A For Column T-102 $ 32,934
23 Condenser
24 Reflux Pump
25 Reboiler
26 Condenser
27 Reflux Pump
$ 1,715,601 $ 4,600,968
Total
32
Table 4.5: Total grass roots plant costs ofthe HDA process

Total Grass Roots Plant Cost S 2,733,000 $ 6,337,000
4.3 Performance Comparison
.\t this point, it is xxorth highlighting the key benefits and disadvantages ofthe
moditied HDA design ox er the conventional one. It is also interesting to examine where
the main economic benefits ofthe modified process arc derived. Table 4.6 provides the
main benefits ofthe modified design, and Table 4.7 highlights the drawbacks ofthe
modified design.
Table 4.6: Benefits ofthe modified design
Modified Design Conventional design

2,092.3 4,743.5
Reactor volume, ft
974.5 4,405.9
Feed rate to separator svstem, Ibmole/hr
Compressor power, hp N/A 1!
N/A Needed
Stabilizing column
Toluene/Diphenyl distillation column N/A Needed
-742 ,440
Profit, $/hr
2,733,000 6,337,000
Grass roots cost ofthe plant, $
Table 4.7: Disadvantages ofthe modified design
Modified Conventional
HDA Process HDA Process
669.46 495.38
Total purge rate, Ibmole/hr
Total hydrogen purged, Ibmole/hr 376.54 206.08
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
Conventional HDA Conventional

process xvith the HDA process
reaction rates used by xvith the adjusted
Luyben et al. [3] reaction rates
Heat of Reaction 1, BTU/lbmole -2.150e+04 -2.108e+04
Heat of Reaction 2, BTU/lbmole 0 1.05e+04
Activation Energy of Reaction 1, cal/mole 5.09e+04 5.09e+04
Activation Energy of Reaction 2, cal/iuole 5.09e+04 3.05e+04
Activation Energy of Reaction 3, cal/mole 5.09e+04 2.47e+04
Pre-exponential reaction rate coefficient
3.69e+06 3.69e+06
of Reaction 1. lbmole/min-ft3-psial.5
5.99e+04 0.6272
of Reaction 2. lbmole/min-ft3-psia2
2.55e+05 0.1011
of Reaction 3. lbmole/min-ft3-psia2
Toluene flow rate from the reactor,
90.64 127.81
Ibmole/lir
Hydrogen flow rate from the reactor,
1,704.26 1,729.61
Ibmole/hr
Benzene flow rate from the reactor, 290.64 289.30
Ibmole/hr
Diphenyl flow rate from the reactor, 4.09 1.8
Ibmole/hr
Methane flow rate from the reactor, 2.282.17 2,257.37
Ibmole/hr
Reactor Volume, ft3 4,743.48 4,743.48
Toluene conversion, % I 75 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).
13 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 Coallar 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.
Input
ill format i o u :
From Figure 3.1 (Chapter 3 ot t h i s work), we have the following value:
Ea2/R v a l u e , degree K: 1 S362e+04
From Luyben et a l . ( 3 1 :
Eal/R value, degree K: 2 5<jl<.>e + 0 4
A2, Ibmole/(min ft3 psia2) 5 987e+ 04
A3, Ibmole/(min ft3 psiaZ) 2 . .55;3e-t 0 5
Ea2/R v a l u e , degree K: 2 5616e-t 0 4
Ea3/R v a l u e , degree K: 2 ? . b l 6 e H- 0 4
Push t h e green arrow t o

c a l c u l a t e the adjusted values.
R e s u l t s ( a d j u s t e d v a l u e s ) of t h i s program:
H e a t of R e a c t i o n 1, (From Luyben et a l . I 3 ] , t h i s
•2 096e+4 value i s -2.1S0e+04 Etu/lbmole)
Btu/Ibmole:
(From Luyben et a l . l 3 ) , t h i s
H e a t of R e a c t i o n 2, 1 118e+4 value i s 0 Btu/lbmole)
Btu/Ibmole:
Ea3/R v a l u e , degree K: 1 2237e+04
Al, Ibmole/(min ft'3 psia-"1.5) 3 6858e+06
A2, Ibmole/(min ft^3 psia'-Z). 0 U21L1
A3, Ibmole/(min ft/-3 p3ia^2): 0 08124
44
The following is the program script for calculating the adjusted kinetic and
themiodynamic parameters of reaction rate expressions using HiQ^' [23].
// WotrftioH.- B a a s a j M (B) / l>l,stbaiis iM) ,• Toluszx i'O,- Hy,Jirot,t?n (H).- Dxph&nyl (Z»
// R a a c t i o n 1: T V- H --•>- B <• M
// ^?toic>ix<?ai«s4ric coefficients f-rjr R « d o t j o « 1 .ii-«:
sTl -1; sHl - - 1 ; sBl 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 d«9-i-«« C i n Jr<5d 1/tto2« f r o a "aASJC PHFSrOli 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 . S Z ;
/ / Hs^t of Rejctioa 1 (d&lt^SRl_Z9SJ aMd P.&actl.c.-3 2 (d«ltaSR2_ZSS) jit 2S asg-retn C in Jôul^/^nale

dell:.aH».l_29S (sTl*Hf_T + sHl*H£_H + sBl*H£_B + sHl»H£_H) »418S. 8 ;
d e l t a H I l 2 _ Z 9 8 " (sH2»H£_H + sB2''H£_B + sD2»Hf_D) * 4 1 8 S . 8 ;
,^/ ld&3il ^^5 ^Ât cutDâ±t±€t3 ,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 . 0 2 S 0 2 ; cD = -7.22a-4; d0 1.42a-7; at> " 3-98e-ll;
aB = 1 8 . S ; bB - - 1 . 1 7 e - 2 ; cB 1.2Sa-3; dB - -2.08e-6; eB - i.OSe-9;
at 31-S; bT -1.6;e~2; cT = 1.448-3, dT • -2.298-6; eT - l-14a-9;
aM 33.4; bH • - 7 . 3 7 a - i ; cH = 2.91e-4; <m = -2.64a-7; eM 8.01e-ll;
aH 17.6; bH «.70e-2; cH -1.31e-4; dH - i.06e-7; aH -i.92e-li
/ / Hedit cf R&^ctio:.!^ afc s p e o i f i e c ? teaperd!*uir«s i « .?'<?Kl«/aiol«

/ / .St r 894. ii K niSO F)
d e l t a H R l _ 8 9 4 = d e l t a H R l _ 2 9 8 t i n t e g r a t e ( c P l , 2 9 3 - I S , 8 9 4 . i S , t r<»i>«eoi«-') ;
/ / ^be f'o2 2 oi^-xi^^r v^ltts i s xn Bfe2.t/2h'J»c>2«
d e l t a H R l _ B t u l b a o l e - d e l t a H A l _ 8 9 4 « <9 . 4 7 8 1 7 1 i 2 0 3 1 3 e - 4 j / 2 . i 0 4 6 2 2 6 2 1 8 S e - 3 ;
function cPKx)
p r o j e c t s T l , s H l , s B l , s H l , a l , aH, a B , aH, b T , bH, b B , bH, c T , cH, oB, cH,
dT, dH, dE, dH, e T , eH, e B , sH;
y = sTl-'CaT + bT*t: + C T ' K ' Z + dT>-!;'-3 + aT*x-4) +
EHl*(aH + b H ' x + cH'::'-2 + dH':t-^3 + eH-»x"4) +
s B l » ( a B + bB*i! + c B ' x ' - ^ + dB*x"3 + eB-*x'-4) +
s H l ^ i a H + bH*x + cH'x--2 + dH*x''3 + e H ' ' x ~ 4 ) ;
return y;
end £«aiction;
// At T ^ 834.26 K (IISO F)
deltaHR2_894 d a l t a H R 2 _ 2 9 8 + i n t e g r a t e I c P 2 , 2 9 8 . 1 5 , 8 9 4 . 2 6 , <t;r.ii>er.oi.i J ;
/ / tij« fclloiviav v a i a e zs ia Btu/li>aole
deltaHR2_Beull.mola deltaHE2_894* (9. 478171220313e-4)/2. 20462eS218Ea-3;
f u n c t i o n cP2(x)
p r o S e c t sHZ, sBZ, 31.2, aH, a B , aD, bH, b B , bD, cH, c E , c f , dH, dB, dK, aH, a B , aD;
y - sHZ'-isH + bH»x + cH»j:-2 <• dH»x"3 4 eH«x^4) +
sB2-*CaB + bE^x + cE-'x'-Z + d E » x ' 3 + K B * X ~ 4 ) +
ED2»taI> t b D ' x f cD*x'-2 + dl'»x~3 + e C x M ) ;
r e t u m y;
end function;
// 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_» Value_of_Ea2_c.ver_P_degK;
deltaHEZ_c'./Br_R deitaHR2_Btuibttole/ (1.987*1.8) ;
Ea3 o v e r _ R - BaZ_over_P d6lcaHP2__over_E;
/ / Thz^ p c r t x o . - . ..t t2-.« s c r x p t 1^ d«:»X9«ad t o =.,2^t.2.,ta tfc^ A2 ^..d i*^ .....2u««
/ / tar tii^ ^dytzst^d r a t e ^xpi'^^-sz'-'"^ „,„,^., , , , .
A2 «>a A2 L u y b a n * e « p < - E a 2 o v a r » _ L u y b a n _ d e , K / 8 9 4 . Z S ) / e ^ i - S a 2 _ o v a r _ E / 8 9 4 . 26) ;
t l > ' = t3:'uyban^JS<-Ka3:o..«rP_Luyb.n_da,K/894.26)/e^(-Ha3_ovar_P./894.26, ;
45
APPENDIX B
ECONOMIC DATA
46
VALUES OF CHEMICAL SPECIES
Table B.l: Toluene and Benzene price information |27, 28|

Specific Water density', Molecular
.Material S/gal S/lb S/lbmole
gravity lb/gal Weight
Toluene 0.76 0.866 8.33 0.105 92 9.66
Benzene 0.80 0.879 8.33 0.109 78 8.52
Hydrogen (95'%) with 5% methane) 1.14
Table B.2: Hydrogen and Methane fuel values information |1|

Material BTU/lbmole* Current Price, $/10''BTU $/lbmole
fiydrogen 1.23E+05 4.00 0.49
Methane 3.83E+05 4.00 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 COMPOSITION
Vapor Phase COMPONENTS MOLE FRACTION
Vapor / Phase Fraction I .()()()() Toluene 0.0000
Temperature: (C) 30.00 Hydrogen 0.9700
Pressure: (psia) 500.0 Benzene 0.0000
Molar Flow (Ibmole/hr) 49(1.4 Methane 0.0300
Mass Flow (kg/min) 9,(134 BiPhenyl 0.0000
Material Stream: Recycle Gas

Vapor Phase COMPONENTS MOLi; FRACTKJN
Vapor / Phase Fraction 1.0000 Toluene 0.0009
Molar Flow (Ibmole/hr) 3519 Methane 0.5602
Mass Flow (kg/min) 276.9 BiPhenyl 0.0000
Material Stream: Sep. bottoms

Liquid Phase COMPONENTS MOLE FRACTION
Molar Flow (Ibmole/hr) 454.6 Methane 0.0519
Material Stream: Sep. inlet

Overall COMPONENTS MOLE FRACTION
0.8978 Toluene 0.0314
Vapor / Phase Fraction
Hydrogen 0.3891
Temperature: (C) 45.00
Benzene 0.0708
Pressure: (psia) 500.0
Methane 0.5082
Molar Flow (Ibmole/hr) 4446
BiPhenyl 0.0004
Mass Flow (kg/min) 586.0
Material Stream: Toluene Feed

Temperature: (C) 26.98 Tlydrogen 0.0000
49
Table C l continued
Material Stream: I
Liquid 1'base COMPONENTS MOLE FRACTION
N'apor / Phase FraL'lion (I 0(100 Toluene 1OOOO
Temperature: (C) 30.00 Hydrogen 0.0(100
Pressure, (psia) 50(1.0 Benzene 0 0000
Molar Flow (Ibmolc'lir) 273 0 Methane 0 0000
Mass Flow (kii iiiui) 19(1.2 Bd^hcnvl 0 (1000
Material Stream: 2
()\ erall COMPONENTS MOLE FRACTION
Temperature: (C) 57.56 Hydrogen 0 4838
Pressure: (psia) .500.0 Benzene 0.0051
Molar Flow (Ibmole/hr) 4LV3 Methane 0.4805
Mass Flow (kg/min) 371.9 BiPhenyl 0,0000
Material Stream: 3
Liquid Phase COMPONENIS MOLE FRACTION
0.0000 Toluene 0.9995
V a p o r / Phase Fraction
T e m p e r a t u r e : (C) 137.8 Hydrogen 0.0000
Material Stream: 3 (Purge)

CONDITIONS C(JMPOSITION
Vapor Phase COMPONENTS MOLT; FRACTION
1.0000 Toluene 0.0009
V a p o r / Phase Fraction
45.00 ll\drogen 0.4329
T e m p e r a t u r e : (C)
Benzene 0.0060
Methane 0.5602
Molar Flow (Ibmole/hr) 472.3
BiPhenyl 0.0000
Material Stream: 4
COMPOSITION
CONDITIONS MOLE FRACTION
gg COMPONENTS
Liquid Phase
Toluene 0.9995
Vapor / Phase Fraction 0.0000
Hydrogen 0.0000
Benzene 0.0005
Methane 0.0000
BiPhenyl 0.0000
Material Stream: 4 (Methane)

COMPOSITION
CONDITIONS MOLE FRACTION
Vapor I'base COMPONENTS
Toluene 0.0000
Hydrogen 0.0688
Temperature: (C) -7.401
Benzene 0.0005
Pressure: (psia) 480.0 0.9307
Methane
Molar Flow (Ibmole/hr) 23.06 0.0000
BiPhenyl
50
T a b l e d continued
Material Stream: 5
Material Stream: 5 (Benzene)

Material Stream: 6
Material Stream: 6 (Diphenyl)

Material Stream: 7
Vapor / Phase Fraction 1.00(10 Toluene 0.0009
Material Stream: 8
51
Table C l continued
Material Stream: 9
Material Stream: 10
Vapor Phase COMPONENTS MOLE FRACTK3N
Temperature: (C) 62 1.1 Hydrogen 0.4538
Material Stream: 11
Material Stream: 12
45.00 Hydrogen 0.0038
Temperature: (C)
500.0 Benzene 0.6403
Pressure: (psia)
40 02 Methane 0.0519
Molar Flow (Ibmole/hr)
23.94 BiPhenyl 0.0044
Mass Flow (kg/min)
Material Stream: 12 1
COMPOSITION
CONDITIONS
Toluene 0.2994
Hydrogen 0.0038
500.0 Benzene 0.6406
Methane
BiPhenyl 0.0044
Material Stream: 13
COMPOSITION
CONDITIONS COMPONENTS MOLE FRAC TION
Vapor Phase
Toluene 0.0314
Hydrogen 0.3891
Benzene 0.0708
Methane 0.5082
Molar Flow (Ibmole/hr) 4446
BiPhenyl 0.0004
^^
Table C.I continued
Material Stream: 14
Material Stream: 15
Material Stream: 16
Liquid Phase CCJMPONENTS MOLE FRACTION
Material Stream: 17
Liquid Phase C()MPONT:NTS MOLE FRACTION
Molar Flow (Ibmole/hr) 391.5 Methane O.OOOI
Material Stream: 18
0.0000 Toluene 0.9852
142.4 Hydrogen 0.0000
Temperature: (C)
33.00 Benzene 0.0005
Pressure: (psia)
126.0 Methane 0.0000
88.64 BiPhenyl 0.0143
Mass Flow (kg/min)
53
Table C.2: Parameters for equipment ofthe conventional HDA process
Compressor
Compressor: K-lOO Adiabatic LIT.: 75.00
Duty: 2.4466e-t-05 cal/min PolyTropic Eff: 75.00
Furnace
Heater: E-101 Pressure Drop: 0.0000 psi
Duty: 9.846e-^007 caLmin
Cooler
Cooler: E-102 Pressure Drop: 0.0000 psi
Duty: 1.194e-H008 cal/min
V-100 (Separator)
Vessel Volume: 276.5 ft3 Pressure Drop: 0.0000 psi
Level SP: 50.00 % Duty: 0.0000 cal/min
Liquid Volume: 138.2 ft3 Heat Transfer Mode: Heatinsj
Vessel Pressure: 500.0 psia
Pumps
Pump: P-100 Delta P 485.3 psi
Adiabatic Efficiency (%): 75.00 Energy: 2.348e+005 calmin
Pump: P-101 Delta P: 470.0 psi
Adiabatic Efficiency (%): 75.00 Energy: L182e+005 cal/min
Heat Exchanger
Heat Exchanger: E-lOO
PARAMETERS
Exchanger Desig n (End Point)
Tube Side DeltaP: 0.0000 psi
Shell Side DeltaP: 0.0000 psi Passes: —
UA: 1.023e-H005 Btu F-hr Tolerance: l.OOOOe-04
Tube Side Data Shell Side Data

Heat Transfer Coefficient — Heat Transfer Coefficient —
Tube Pressure Drop 0.00 psi Shell Pressure Drop 0.00 psi
Fouling 0.00000 F-hr-ft2/Btu Fouling 0.00000 F-hr-ft2/Btu
Tube Length 19.69 ft Shell Passes 1
Tube O.D. 0.79 in Shell Series 10
Tube Thickness 0.0787 in Shell Parallel 1
Tube Pitch 1.9685 in Baffle Type Single
Orientation Horizontal Baffle CutC'oArea) 20.00
Passes Per Shell 6 Baffle Orientation Horizontal
Tubes Per Shell 156 Spacing 31 4%l in
Layout Angle Triangular (30 degrees) Diameter 28.7430 in
TEMA Type A E L Area 633.03 ft2
54
Table C.2 continued
Plug Flow Reactor

Plug Flow Reactor: PFR-lOO
Physical Parameters
Type : User Specified Pressure Drop: 0.0000 psi Heat Transfer: Heating
T\ pe Direct Q Value Energy Stream : Q Reactor Duty : 0.0000 cal/min
Dimensions
Total Volume: 4066 ttj
Length: 57.00 ft
Diameter: 9.530 ft
Number of Tubes: 1 Wall Thickness: 1.640e-002 ft
Void Fraction: 1.0000 Void Volume: 4(166 rt3
Reaction Info
Reaction Set: Global Rxn Set Initialize From: Current
Integration Information
Number of Segments: 20 Minimum Step Fraction: l.Oe-06 Minimum Step Length: 5.7e-05 ft
R,\n-1 (Kinetic): Stoichiometry, Basis, Parameters
STOICHIOMETRY
Component Molecular Weight Stoich Coeff Forward Order Reverse ()rder
Toluene 92.14 -1 1.000 (1 0000
Hydrogen 2.016 -1 0.5000 0.0000
Benzene 78.11 1 0.0000 0.0000
Methane 16.04 1 0.0000 0.0000
Balance Error : 0.0000 Reaction Heat: -1.804c 1004 Btu/lbmole
BASIS
Basis Base Component Rxn Phase Min. Temp (C) Max. Temp(C)
Partial Pres Toluene VapourPhase -273.1 3000
PARAMETERS
Forward Reaction Reverse Reaction
A : 3.686e-H006 A': —
E:9.157e-004 E':—
Rxn-2 (Kinetic): Stoichiometry, Basis, Parameters
STOICHIOMETRY
Component Molecular Weight Stoich Coeff Forward Order Reverse Order
Benzene 78.11 -2 2.000 0.0000
BiPhenyl 154.2 1 0.0000 1.000
Hydrogen 2.016 1 0.0000 1.000
Balance Error: 0.0000 Reaction Heat: 3490 Btu/lbmole
BASIS
Basis Base Component Rxn Phase Min. Temp (C) Max. Temp (C)
Partial Pres Benzene VapourPhase -273.1 3000
PARAMETERS
Forward Reaction Reverse Reaction
A : 0.6272 A': 0.08124
E : 5.495e-H004 E' : 4.447e+004
55
T a b l e C.2 continued
Distillation C o l u m n s
Distillation: T-100
Tra\ Summary
Flow Basis: Molar
Reflux Ratio: 3.000
Temp. Pressure Liquid Vapor Feeds Draws Duties

(C) (psia) (Ibmole/hr) (Ibmole/hr) (Ibmole/br) (Ibmole/hr) (cal/min)
Condenser 102,5 30.00 796.4 — —. 265,5 L -5.715e+(107
1 M;iin TS 104 0 30.00 801.8 1062
2 MLiin IS 104 2 30.12 801.8 1067
3 Main TS 104 ^ 30 23 801.7 1(167
4 _ M a i n TS 104 5 30-35 801 5 1067
5 Main IS 104 7 30 46 801.0 1067
(1 MainTS 105.0 30-58 800.1 1066
7 Mam TS 105,4 30.69 798.4 1066 ___
8 MainTS 105.9 30,81 795,4 1064 —
4 MainTS 106.8 30.92 79(1 4 1061 —-
10 MainTS 108.2 31 04 782.8 1056 —
11 Main IS 110 2 31.15 772.7 1(148 —
12 MainTS 112.9 31 27 761.3 1038 —
13 Main TS 116.1 31 38 751.0 1027 —
1 4 _ M a i n IS 119.3 31.50 742 9 1016 —
15 Main TS 122 2 31.62 741.3 1008 391.5 L
16 MainTS 126 3 31.73 737 1 615.3 —
r MainTS 130.4 31.85 735 2 611.0 —
18 MainTS 133,9 31-96 735 4 609 2 ...
19 MainTS 136.6 32.08 736 4 609 3 ...
20 Mam TS 138.4 32 19 737 6 610 4 ...
2 1 Main TS 139.6 32.31 7-i8.6 611.6 ...
22 Mam TS 140 4 32 42 739.3 612.5 ...
23 Main TS 140,9 32.54 739.9 613.3 —
2 4 _ M a i n TS 141.2 32.65 740.3 613.8 ...
25 Main TS I4I.5 32.77 740.7 614 3 —
26 Main TS 141.7 32.88 741.0 614 6 ...
2 : ' _ M a i n TS 141.9 33.00 740.3 614 9 —
; Reboiler 142 4 33.00 — 614 2 — 126,0 1. 3.556e+007
Distillation: T-IOI
Tray Summary
Tlou Basis: Molar
Reflux Ratio: 0.5000
(C) (psia) (Ibmole/hr) (ibmole/hr) (Ibmole/hr) (Ibmole/hr) (cal/min)
Condenser 137 8 30.00 61.75 — — 123,5 L -1 076c+(HI7
1 Main TS 137.8 30.00 61.56 185.3 —
2 Main TS 138.1 30.17 61 46 185.1 ...
3 Mam TS 138.3 30.33 61 34 1X5.0 ...
4 Main TS 138.6 30.50 6(1.90 1X49 ...
5 _ M a i n TS 139.2 M) 67 1X4 4 184.4 126.0 L
6 Main TS 139.5 30.83 181.7 181,9 —
7 Main I S 143.0 31.00 140.9 179,2 —
Reboiler 196,0 31.00 — 138 4 — 2.540 L 1.063e+007
56
Table C2 continued
T-102 (Shortcut Column)

PARAMETERS
Component Mole Fraction
Light Ke\ Methane 1 .OOOe-004
HeavN Ke\ Benzene 5.000e-004
Pressures (psia) Retlux Ratios

Condenser Pressure 480.0 Extemal Retlux Ratio 0.2000
Reboiler Pressure 480.0 Minimum Retlux Ratio 2.151e-002
RESULTS
Trays / Temperatures Flows
Minimum # of Tra\s 2 546 KcctiT\ Vapor (Ibmole/hr) 27.68
Actual # of Tra\s 6.182 Rectify Liquid (Ibmole/hr) 4.613
Optimal Feed Stage 3.758 Stripping Vapor (Ibmole/hr) 27.68
Condenser Temperature (C) -7.401 Stripping Liquid (Ibmole/hr) 419.2
Reboiler Temperature (C) 268.1 Condenser Duty (cal/min) -6.542e+005
Reboiler Duty (cal/min) 3.025e+007
57
The following is the reactor information in the conventional HDA process.
Inlet Outlet
Temperature 1150 F Temperature pî F
Pressure 500.0 psia Pressure 500.0 psia
Molar Flow 4383 Ibmole/lir Molar Flow 4383 Ibmole/lir
Comp Mole Frac (Toluene) 0,0856 Comp Mole Frac (Toluenei 0.0307
Comp Mole Frac (Hydrogen) 0.4291 Comp Mole Frac (Hydrogen i 0.3745
Comp Mole Frac (Beiêne) 0.0053 Comp Mole Frac (Benzene) 0.05%
Comp Mole Frac (Methane) 0.4800 Comp Mole Frac (Methane) 0.5350
Comp Mole Frac (BiPhenyl) 0.0000 PFR-100 Comp Mole Frac (BiPhenyli 0.0003
Outlet
PFR-100 Reactor Q
Pressure Drop 0.0000 kPa
Heat Flow 0.0000 kJ/h
Reactor Q
Reactor Volume 1154 m3

Heat Flow 0.0000 kJ/h
Bed Voldage 1,0000
10 20 30 40 60
Reactor length, ft
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 "Reaction-1
2 3.00E-02 ' Reactions-2&3

•-+
c
2.00E-02
o
« 1.00E-02
O.OOE+00
10 20 30 40 50 60
Reactor length, ft
Figure C.2: Reaction rates in the reactor ofthe conventional HDA process
6.00E-01
5.00E-01
4.00E-01 -•—Toluene
-m- Hydrogen
u
ra 3.00E-01 ~^-- Benzene
-^<—Methane
o
2.00E-01 -^te-Diphenyl
1 OOE-01
O.OOE-t-00 -)i<:>>:x**?>»:*:x^>»:>K'^»^*^^'<*^*^^
10 20 30 40 50 60
Reactor Length, ft
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
Equipment B are Module

Equipment Label*
Cost** Cost***
1 Feed Pump P-100 S 20.432 $ 67.(i28
-) Heat Exchanger E-lOO % 167.332 $ 1.14(1.188
3 Furnace K-101 s 2(1^).451 S 791.724
4 Reactor(s) PFR-lOO \ 5 1.49(1 s 912.985
5 Cooler i:-i(i2 $ 2(1.471 $ 89,563
6 Separator v-100 s 5S.219 $ 419.924
7 Stabilizer Column r-i(i2 $ 35.V20 $ 196,385
8 Product Column T-IOO $ (i2.0?i) $ 216,767
9 Recycle Column l-IOl s 22.892 $ 73,208
10 Recycle Pump p-101 t. 17.108 $ 56,626
11 Recycle Compressor R-KMl $ 83.585 $ 22(1.619
i : Reboiler tor C olumn 1 -100 $ 1(1.1 12 $ 53.169
13 Condenser for Column T-IOO $ 21,066 $ 65.094
14 Reflux Pump for Column T-100 $ 9.538 $ 31,570

$ 9,980 $ 32,934
15 Reboiler for Column 1-102
$ 19.452 $ 82,087
16 Condenser for Column 1 -I(i2
% 9,538 $ 31.570
1" Reflux Pump for Column T-102
$ 7,329 $ 24,185
18 Reboiler for Column 1 -101
$ 12.12(1 $ 5 1,1 72
19 Condenser for Column 1 -101
9.538 $ 31.570
20 Reflux Pump for Column 1 -101 s
s 869,638 $ 4,600,968
* See Flow Diagram for the conventional HDA process (sec Chapter 2)
** - Equipment Cost - equipment cost data adjusted for any difference in unit capacil\
and elapsed time since the cost material « a s generated (usmg cost Index)
*** - Bare Module Cost - the sum o f t h e 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, msurancc. and taxes
b. Construction o\ erlicad
c. Contractor engmcering 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 Number of Spares = 0
Reciprocating Compressor/Blower Equipment Cost = $ 72 316
Power (kW) = 90 Bare Module Cost = $ 209 716
Material of Construction = CS
DRIVES
Drive. D-101 Number of Spares =0
Compressor and Blower Drives - Electric - E.xplosion Proof Equipment Cost = $11 269
HEAT EXCHANGERS
Heat Exchanger. E-101 Tube Side Pressure (barg) =37
Shell and Tube - Fixed Tube Sheet Shell Side Pressure (barg) =37
Area (m2) =2 787.0912 Equipment Cost = $ 167 332
.Material of Construction =SS SS Bare Module Cost = $ 1 146 188
Heat Exchanger, E-102 Kettle Reboiler Shell Side Pressure (barg) =1
Area (m2) =50 Equipment Cost = $ 16 112
Material of Construction =CS CS Bare Module Cost = $ 53 169
Tube Side Pressure (barg) =1
Heat Exchanger. E-103 Kettle Reboiler Shell Side Pressure (barg) =1
Material of Construction =CS'CS Bare Module Cost = $ 32 934
Heat Exchanger. E-105 Air Cooled Exchanger Pressure (barg) =1
Material of Construction =CS Bare Module Cost = $ 28 068
Heat Exchanger, E-106 Air Cooled Exchanger Pressure (barg) =1
Area (m2) =10 Equipment Cost = $ II 145
Material of Construction CS Bare Module Cost = $ 28 068
Heat Exchanger, E-107 Air Cooled Exchanger Pressure (barg) =1
Area (m2) =10 Equipment Cost = $11 145
Material of Construction =^CS Bare Module Cost = $28 068
Heat Exchanger, E-108 Tube Side Pressure (barg) =36
Material of Construction SS SS Bare Module Cost = $ 54 336
FIRED HEATERS
Heater, H-l01
Tube Material of Construction= SS
Non-Reactive Fired Heater
Equipment Cost = $ 209 451
Duty (kW) =984 Bare Module Cost = $ 791 724
Tube Pressure (barg) =200 barg
PUMPS
Pump, P-101 Suction Pressure (barg) = I
Centrifugal Pump Number of Spares = I
Material of Construction = Cast Iron Equipment Cost = $ 20 432
Power (kW)= 16.23 Bare Module Cost = $ 67 628
Pump. P-102 Suction Pressure (barg) = 1
Centrifugal Pump Number of Spares = 1
Material of Construction • Cast Iron Equipment Cost = $ 9 538
Power (kW) = 2 Bare Module Cost = $31 570
Pump, P-I03 Suction Pressure (barg) = I
Material of Construction = Cast Iron EquipmentCost = $ 9 538
Pump, P-104 Suction Pressure (barg) = I
Material of Construction = Cast Iron Equipment Cost = $ 9538
Power(kW) = 2 Bare Module Cost = $31 570
Material of Construction •• Cast Iron EquipmentCost = $ 9 538
Pump, P-106 Suction Pressure (barg) = 1
Power (kW) = 2 Bare Module Cost - 5> 3 1 570
Material of Construction = Cast Iron EquipmentCost = $ 9 538
Power(kW) = 2 Bare Module Cost = $ 31 570
62
Material of Construction ^ Cast Iron Equipment Cost = $ 16 966
Power (kW)= 10 Bare Module Cost = $ 56 156
TOWERS
Tower, T-101 Number of Trays =15
Tower Material of Construction= CS fia\ Material of Construction= CS
Diameter (m) =1.524 Vessel Cost = $ 58 625
Height/Length (m) =20 Internals Cost = $ 0
Pressure (barg) =1 Bare Module Cost = $ 247 398
Tower, T-102 Number of Trays =7
Tower Material of Construction= CS Tray Material of Construction= CS
Diameter (m) =0.9144 Vessel Cost = $ 10 498
Height/Length (m) =4.27 Internals Cost = $ 0
Pressure (barg) = 1 Bare Module Cost = $ 44 302
\ESSELS
Process Vessel, V-IOI Height/Length (m) = 17.37
Material of Construction = SS Pressure (barg) = 37
Vessel Orientation = Horizontal Equipment Cost = $51 490
Diameter (m) = 2.90 Bare Module Cost = $ 912 985
Process Vessel, V-102 Height/Length (m) = 16.02
Material of Construction = SS Pressure (barg) = 35
Vessel Orientation = Horizontal Equipment Cost = $ 5 155
Process Vessel, V-103 Height/Length (m) = 10
Material of Construction = CS Pressure (barg) = 1
Vessel Orientation = Vertical Equipment Cost = $31 542
Process Vessel, V-104 Height Length (m) = 3
Vessel Orientation = Vertical Equipment Cost = $ 19 452
Diameter (m) = 2 Bare Module Cost = $82 087
Diameter (m) = 2 Bare Module Cost = $ 82 087
Material of Construction = CS Pressure (barg)= 1
Vessel Orientation = Vertical Equipment Cost = $ 19 4.^2
63
Table C.4: Operating cost summary for the conventional HDA process
BTU/hr Dollars/hr*
Electrical power:
K-lOO 5.K2E+04 0.68
P-100 5.59E+04 0.65
P-101 2,8ir-+04 0.33
Fuel (Oil or Gas):
E-101 2.34E+07 93.77
Cooling water:
E-102 2.85E+07 0.53
T-100 Condenser 1.36E+07 6.77
T-101 Condenser 2.56E+06 1.28
T-102 Condenser 1.56E+05 0,08
Steam
T-lOORebolier 8.47F.+06 435.68
T-101 Rebolier 2.53E+06 130,24
T-102Rebolier 1 7.20E+06 370,62
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: Benzene Product
CONDITIONS COMPOSIIION
Liquid Phase COMPONI:N IS MOLE FRACTION
Vapor / Phase Fraction 0.0000 I'oluenc
Temperature: (F) 0.0000
165 5 1 lydrogen 0.0000
Pressure: (psia) 14.70 Benzene
265.0 Methane (1.0002
Mass Flow (lb hr) 2 070c+(104 UiPhcnyl 0.0000
Material Stream: Fresh Hydrogen
N'apor / Phase Fraction 1.0000 Idluenc 0.0000
Temperature: (F) 86.00 Hydrogen 0 9700
Pressure: (psia) 500.0 Benzene 0 OOOO
Mass Flow (Ib/hr) 1622 BiPhenyl 0.0000
Material Stream: Fresh Toluene
\'apor / Phase Fraction 0.0000 toluene 1.11000
Temperature. (F) 77.0(1 1 Kdrogen 0.0000
Pressure: (psial 14 70 Benzene 0.0000
Molar Flow (Ibmole'hrl 268.9 Methane 0.0000
Mass Flow (Ih'hr) 2.478e+004 BiPhenyl 0.0000
Material Stream: Fumace
CCJXDITIONS COMPOSITION
Vapor / Phase Fraction 1.0000 1oluene 0.0003
Temperature: (F) 77,96 II\drogcn 0.0754
Pressure, (psia) 14 70 Benzene 0.1191
Molar Flow (Ibmole/hr) 12.93 Methane 0 8053
Ma.ss Flow (Ib/hr) 289.6 liiPhenvl 0.0000
.Material Stream: Methane out
Temperature: (1 ) 166.7 1 lydrogen 0.0008
.Molar Flow (Ibmole/hr) 4 486 Methane 0.1143
Mass I low (Ib/hr) 318 3 BiPhenvl O.OOOO
Material Stream: To membrane Unit

Vapor Phase COMPONENTS MOLE F R A C U O N
Vapor / Pha.se Fraction 1.0000 toluene 0 OOOO
temperature: (F) 80.00 1 lydrogen 0 5720
Pressure: (psia) 496 6 Benzene 0.0038
Vlass Flow (Ib/hr) 5418 Bil^henyl 0 OOOO
66
Table D, 1 continued
Material Stream: I
C(WDIT10NS COMPtJSniON
Vapor I'liasc COMPONENTS MOLE FRACTION
Vapor / Phase Fraction 1.0000 I oluene 1.0000
Temperature: (F) 710.0 I l\dr(i)icii 0.0000
Mass Flow (Ib/hr) 826(1 BiPhenvl 0.0000
Material Stream: 2
Vapor Phase COMPONENTS MOLL FRACTION
\ apor / Phase Fraction 1.0000 Toluene 1.0000
1 cmperature: (F) 710.0 tlydrogen O.OOOO
Pressure: (psia) 499.5 Benzene O.OOOO
Mass Flow (Ib/hr) 826(1 BiPhenyl 0.0000
Material Stream: 3
Vapor / Phase Fraction 1 OOOO Toluene 1.0000
Temperature: (F) 710.0 Hydrogen 0.0000
Pressure: (psia) 499 5 Benzene 0 OOOO
Molar Flow (Ibmote/hr) 89.67 Methane 0,0000
Mass Flow (tb/hr) 8262 BiPhenvl 0 OOOO
Material Stream: 4
\ apor Phase COMP()Nt-;NTS MOLE FRACTION
\ apor / Phase Fraction 1 00(10 loluene 1.0000
femperature: (F) 835 1 Hydrogen 0.0000
Molar Flow (Ibmole hr) 89.64 Methane O.OOOO
Vlaterial Stream: 5
Overall COMPONENIS MOLE FRACTION
Vapor / Phase Fraction 0 6322 Toluene 0.0059
Temperature: (F) 80 00 1 lydriigcn 0 3628
Pressure: (psia) 496 6 Ben/ciic 0.3106
.Molar Flow (Ibmole/hr) 1039 Methane 0.2803
.Mass Flow (Ib/hr) 3.767e+004 BiPhenvl 0 0404
Material Stream: 6
CONDHIONS (OMI'OSITION
Vapor Phase C(.)MPONENTS MOLE FRACTION
Vapor / Phase Fraction 1 OOOO 1 <iluene 0.0004
Temperature: (F) 1300 tlydrogen 0.5100
Mass Flow (Ib/hr) 2 400e+()04 BiPhenyl 0.0280
67
T a b l e D.l continued
Material Stream- 7
CCWDITIONS COMPOSiriON
Vapor Phase COMPONENTS MOLE l-RACI ION
N'apor / Phase Fraction 1.0000 Toluene 1.0000
temperature: (F) 976.6 Hydrogen 0.0000
Pressure: (psia) 499 4 tienzene 0.0000
Molar Flow (tbmole/hr) 89.67 Methane 0 OOOO
Material Stream: 8
Vapor Pha.se COMPONENTS MOLE FRACTION
\'apor / Pha.se Fraction 1.0000 Toluene 0 0924
temperature: (F) 1231 11\ drogcn 0 46.^t
Molar Flow (Ibmole hr) 974 5 Methane 0-2094
Mass Flow (Ib/hr) 3.226e-i-004 BiPhenyl 0-0254
Material Stream: 9
Vapor / Phase Fraction 0.0000 Toluene 0 1270
Pressure: (psia) 500-0 Benzene 0.0001
Molar Flow (Ibmole/hr) 40-04 Methane 0.0000
Mass Flow (Ib/hr) 5859 liiPhenyl 0.8729
Material Stream: 10
Liquid Phase (OMPONLNTS MOLl-; FRACTION
Vapor / Phase Fraction 0.0000 I (ilucne 0.0160
Temperature: (F) 80.00 I lydrogen 0 0031
Pressure' (psia) 496.6 Benzene 0.8380
Molar Flow (Ibmote/hr) 382.0 Methane 0 0329
Ma,ss Flow (Ib/hr) 3.225e+0(14 BiPhenyl 0 1099
Material Stream: 11
Liquid Phase COMPONt-NTS MOLE FRACTION
Vapor / Phase Fraction 00000 Toluene 1.0000
S2 46 Hydrogen 0.0000
Temperature: (F)
500.0 Benzene 0.0000
Pressure: (psia)
268.9 Methane 0.0000
Molar Flow (Ibmote/hr)
2.478C+004 BiPhenvl 0,0000
Mass Flow (Ib/hr)
Vlaterial Stream: 12
COMPOSITION
CONDITIONS
0 00(10 Toluene O.OOOO
166,7 Hydrogen 0 OOOO
Temperature: (F)
14 70 Benzene 0 9997
Pressure: (psia)
261.1 Methane 0.0002
2.039e+OO4 BiPhenyl 0.0000
Mass Flow (lb hr)
68
Table D.l continued
Material Stream: 13
0 \ erall COMPONI.NIS MOLIM-RACIION
N'apor / Phase Fraction 0.9262 Toluene 0 1191
Temperature: (F) 392 0 Hydrogen 08118
Pressure: (psia) 499 5 Bcn/enc 0.0000
Molar Flow (tbmole/hr) 795.1 Methane 0.0251
Mass Flow (tb/hr) I 574c K104 BiPhenyl 0 0440
Material Stream: 14
Vapor 1 'base COMPONENTS MOLE FRACTION
\ a p o r / Phase Fraction 1 OOOO Toluene 0.1191
Temperature (F) 1178 Hydrogen 0.8118
Pressure: (psial 498.5 Benzene 0.0000
Molar Flow (Ibmote'hr) 795 I Methane 0.0251
Mass Flow (tb/hr) 1 574e 004 BiPhen\i 0(1440
Material Stream 15
\ apor / Phase Fraction 0.0000 1 oluciic 0.1270
Molar Flow (tbmole/hr) 40 04 Methane 0.0000
Mass Flow (tb/hr) 5859 BiPhenyl 0.8729
Material Stream: 16
\'apor / Phase Fraction 1-0000 Toluene 0 0276
Temperature: (F) 1300 1 lydrogen 0.7060
Pressure: (psia) 498 4 tênzene 0.120(1
Mass Flow (Ib/hr) 1 574c*0(14 BiPhenyl 0 0298
Material Stream: 17
Vapor / Phase Fraction t-00(10 Toluene 0.0052
Temperature: (F) 1300 Hydrogen 0.3864
Pressure:(psia) 498-1 Benzene 0.2760
Mass Flow (Ib'hr) 3.226e+004 BiPhenvl 0.0359
Material Stream 18
CCJND1T10NS COMPOSITION
Liquid Phase COMlÔNENTS MOLE FRACTION
Temperature: (F) 386.2 H>drogen 0 0000
69
Table D.l continued
Material Stream: 19
CONDITIONS
COMPOSITION
Temperature: (F) 1176 t lydrogen 0 6345
Pressure:(psia) 49S4 Benzene 0,1078
Molar Flow (tbmote.'hr) 884.8 Methane 0 1049
Mass Flow (tb/hr) 2.40()e+()04 BiPhenyl 0,0267
Material Stream: 20
CONDITIONS COMPOSITICJN
V apor / Phase Fraction 0 0388 Toluene 0.016(1
Molar How (Ibmole hr) 318.0 Methane 0.0329
Mass Flow (lb,hr) 2.684e+004 BiPhenyl 0.1099
Material Stream: 21
CCWDITIC^NS COMPOSITION
0 \ erall COMPONENTS M O L E F R A C TION
V apor / Phase Fraction 0.8326 Toluene 0 0059
Temperature: (F) 344 1 1lydrogen 0.3628
Pressure (psia) 497 1 Benzene 0.3106
Molar Flow (Ibmolehr) 1039 Methane 0.2803
Mass Flow (tb/hr) 3.767e+0(14 BiPhenyl 0.0404
Material Stream, 22
Vapor / Phase Fraction 1 OOOO Toluene 0.1191
Temperature: (F) 1130 1 lydrogen 0.8118
Molar Flow (Ibmote/hr) 795.1 Methane 0.0251
Mass Flow (Ib hr) 1 574c^004 BiPhenyl 0 0440
Material Stream: 2 3
CONDITIONS COMPOSI 1 ION
V a p o r / P h a s e Fraction 0 0000 Toluene 0.0000
Temperamre: (F) 80.00 t1>clrogen 0.0000
Molar Flow (Ibmote/hr) 3.899 Methane 0.0018
Vlass Flow (tb/hr) 304 1 BiPhenvl 0.0000
Vapor / Phase Fraction 0.1309 1 oluene 0.0000
Temperature: (F) 80 00 Hydrogen 0.0008
Pressure: (psia) 14.70 lienzene 0,8848
Mass Flow (tb/hr) 318.3 BiPhenyl 0,0000
70
T a b l e D.l continued
Material Stream: 25
\ a p o r Phase COMPONENTS MOLE FRAC HON
Vapor / Pha.se Fraction 1.0000 loluene 0.0059
Pressure (psia) 49S 1 Benzene 0.3106
Molar Flow (tbmole/hr) 1039 Methane 0 2803
MiLss Flow (Ib/hr) 3.767e+004 BiPhenyl 0.0404
Material Stream: 26
Liquid Phase COMPONENTS MOLE FRAC t30N
Vapor' Phase Fraction 0,0000 Toluene 0.0167 i
Temperature: (F) 77.85 tlydrogen 0.0000 I
Molar Flow (Ibmolehr) 305.6 Methane 0.0019
NLissFlow (thhr) 2.657c + (l(14 BiPhenyl 0.1144
Material Stream: 27
Temperature: (F) 80.00 ll\drogen 0.0063
Pressure:(psia) 14.70 Benzene 0.1321
Mass Flow (tb/hr) 14.18 BiPhenvl 0.0000
Material Stream: 28
CONDITIONS COMPOS1TKW
Vapor / Phase Fraction 1.0000 Toluene 0,0003
Pressure: (psia) 14,84 Benzene 0.1185
Molar Flow (tbmole/hr) 12,34 Methane 0 8026
Mass Flow (tb/hr) 275,4 BiPhenyl 0.0000
Vapor / Phase Fraction 1,0000 Toluene 0.0059
Viotar Flow (Ibmole/hr) 1039 Methane 0.2803
Mass Flow (Ib/hr) 3.767C+004 BiPhenvl 0.0404
CONDITIONS CO VI POSITION
Vapor Phase Fraction 0.0000 Toluene 0.0160
temperature (Fl 80 04 11\ drogcn 0.0031
Vlotar Flow (tbmole/hr) 382.0 Methane 0.0329
V-lass Flow (Ib/hr) 3 225e + (l04 BiPhenvl 0.1099
71
Table D.l continued
Matcn.il Stream 31
Vapor Phase COMlÔNI'NTS MOLE FRACTION
Vapor / Phase Fraction 1.0000 Toluene 1 000(1
Temperature: (F) 7100 Hydrogen O.OOOO
Molar I'low (tbmole/hr) 268.9 Methane 0.0000
Mass Flow (Ib/hr) 2 478e*004 BiPhenvl 0 0000
Material Stream: 32
Liquid Phase COMPONENl S MOLE FRAC HON
N'apor / Phase Traction 0.0000 Toluene 0.0160
Temperature: (F) SO 04 1 lydrogen 0 0031
Pressure: (psia) 50(1 0 Benzene 0 8-^SO
Molar Flow (Ibmote/hr) 31S0 Methane 0.(1329
1 Mass Flow (tb/hr) 2.(iS4c>004 BiPhcn\l 0 1099
Material Stream: 34
\'apor / Phase Fraction 0.0000 Toluene 0.0160
Temperature: (F) 80.04 1 lydrogen 0.0031
Pressure;(psia) 500 0 Benzene 0.8380
Mass Flow (tb/hr) 5403 BiPhenyl 0.1099
Material Stream: 36
Liquid Phase COMPONENTS M O L E I-RACTION
\ a p o r / Phase Fraction 0 000(1 Toluene 0 0160
80 04 11> drogcn 0 0031
1 Temperature: (F)
500.0 Benzene 0.8380
i Pressure: (psia)
64 00 Methane 0.0329
5403 BiPhenyl 0.1099
Mass Flow (tb/hr)
72
T a b l e D.2: Parameters for e q u i p m e m o f t h e moditied HDA
process
Separators
Separator: V-tOO
Vessel Pressure' 496.6 psia
N'essel Volume: 185.2 ft3
Pressure Drop: 0 OOOO psi
1 cvcl SP: 50.00 "n
t)ut> 0.0000 Btu/hr
Liquid Volume: 92.60 rt3
Heat Transfer Mode: Fleating
Separator- V-101
Vessel Pressure 14 70 psia
Vessel Volume: 4.320 rt3
Pressure Drop: 0.0000 psi
l.e\el SP: 50.00 "o
Duty: 0.0000 Btu/hr
Liquid Volume: 2.160 tt3
Heat Transfer Mode: Heating
Separator: V-102
Vessel Pressure: 14.84 psia
\ e s s e l Volume: 116.6 1^3
Pressure Drop: 0.0000 psi
Le\el SP' 50.00 "o
Duty: 0.0000 Btu/hr
Liquid \ olume: 58 32 03 Heat TransTer Mode. Heating
Heat Exchangers
Heat Exchanger: E -too
Exchanger Design (End Point)
Shell Side DeltaP: 0.5000 psi 1 asses ---
CA l.080e+005 Btu/F-hr
Tolerance: 1 OOOOi'-04
Heat Transfer Coefficient Heat TransTer Coefficient
Tube Pressure Drop0.50 psi Shell Pressure Drop0.50 psi
Fouling 0.00000 F-hr-t't2/Btu Fouling 0.00000 !-hr-ft2/Btu
Tube Length 19.69 ft Shell Passes 1
Tube O.D. 0.79 in Shell Series 5
Tube Thickness 0-0787 in Shell Parallel 1
Tube Pitch 1 9685 in Battle 1 \pe Siimle
Orientation Horizontal liaftleCulC'i.Aica) 20.00
Passes Per Shell 2 BaTtle (Jrientation Honzontal
1 ubes Per Shell 160 Spacing 31 49(il m
Layout Angle Triangular (30 degrees) Diameter 29 (1964 in
TEMA Type AEL .Area (i49 26 Tt2
Heat Exchanger: I -105
Exchanger Design (End Point)
Shell Side DeltaP: 0.5000 psi Passes: —
UA: 1.2096-1-005 Btu/F-hr
Tolerance: 1.0000 >(14
Heat transfer Coefficient Heat Transfer Coet'tlcient
Tube Pressure Drop0.50 psi Shell Pressure Drop0.5(l psi
Fouling 0.00000 F-hr-ft2/Btu l-outing 0 00000 F-hr-ft2/Btu
Tube Length 19 69 ft Shell Passes 1
tube O.D. 0 79 in Shell Series 4
Tube Thickness 0.0787 in Shell târallel 1
Tube Pitch 1 9685 in Baffle Type Single
Orientation Horizontal Baffle CutC'oArea) 20.00
Passes Per Shell 2 liaffle (Jrientation Horizontal
Tubes Per Shell 160 Spacing 31.4961 in
Layout Angle Triangular (30 degrees) Diameter 29.0964 in
TEMA Type AEL Area 649 26 rt2
73
T a b l e D.2 continued
Pluo Flow Reactors

Plug Flow Reactor: PFR-lOO Total Volume: 311.0ft3
T.\ pe User Specified Length: 229.9 ft
Pressure Drop: 0.1000 psi Diameter: 1.312 ft
Heat Transfer : Heating Number of Tubes: 1
T\ pe : Direct Q Value Wall Thickness: L640e-0(J2 ft
Duty . 0.0000 Btu/hr Void Fraction: 1.0000
Plug Flow Reactor: PFR-101 Total Volume: 1159 ft3
Physical Parameters Length: 857.(1 ft
T\pe : User Specified Diameter: 1.312 ft
Pressure Drop: 0.2000 psi Number of'Tubes: 1
Heat Transfer : Heating Wall Thickness: 1.640e-002 ft
T\pe : Direct Q Value Void Fraction: 1.0000
I)ut> : 0.0000 Btu/hr
Plug Flow Reactor: PFR-102 Total Volume: 622.0 ft3
Physical Parameters Length: 459.9 ft
Type : User Specified Diameter: 1.312 ft
Pressure Drop: 0.1000 psi Number of Tubes: 1
Heat Transfer : Heating Wall Thickness: 1 64(le-0()2 ft
T\pe : Direct Q Value Void Fraction: 1.0000
Duty : 0.0000 Bfti/hr
Distillations
Distillation: T-100
Tra\ Summary
Flow Basis: Molar
Reflux Ratio: 2.500

(F) (psia) (Ibmole/hr) (Ibmole/hr) (Ibmole/hr) (Ibmole/hr) (Btu/hr)
166.7 14.70 664.0 — 4.486 V -1.248e+007

Condenser
261.1 L
l^VlainTS 173.7 14.70 676 2 929.6
2_MainTS 173.7 14 70 676 2 941.8
.i^Vlain TS 173.8 1471 676.1 941.8
4_MainTS 173.8 14 72 676.1 941.7
5 _ M a i n TS 173.9 14 73 675 9 941.7
174.0 14 73 675.6 941 5
6 Main TS
174 2 14 74 675 1 941 2
^^VlainTS
174 5 14 75 674.0 940,7
8_Vlain TS
14.76 669 9 939.5
9 _VIain TS 175.1
1047 935 5 305.6
lO^VIainTS 177 2 14.77
1027 1007
1 l _ M a i n TS 182.9 14.77
1005
987.1
12_MainTS 193.2 14.78
965.1
13__MainTS 206.5 14.79 991.3
951.3
14_MainTS 218.2 14.80 988.2
948,2
1 5 _ M a i n IS 226.0 14 80 990.(1
949,9
1 6 _ M a i n TS 230,3 14.81 992.0
17__Main TS 232.3 14.82 993 3 952 0
233.3 1483 993.4 953 2
18 Main TS
234.0 14.84 962.8 953,3
19 Main TS
248.3 14X4 680.2 922,8
20 Main TS 40 04 1.413e-i-007
381.9 14 84 — 64(1 2
Reboiler
74
T a b l e D.2 continued
Heaters
Heater: E-101 Pressure Drop (1 1000 psi
Duty: 5 713e+005 Btu/hr
Heater: E-102 Pressure Drop: 0.1000 psi
Duty: 1.260e-i-006 Btu/hr
Heater: Fumace Pressure Drop: 0.5000 psi
Duty: 6.620e-F005 Btu/hr
Coolers
Cooler: E-103 Pressure Drop: 0.5000 psi
Dut\-: 7.700e+006 Btu/hr
Cooler: E-104 Pressure Drop: 0.0000 ps
Dutv 6,394e+0(l4 Btu/hr
Pumps
Pump: P-100 Delta P: 485 2 psi
Adiabatic Efficiency (%): 75.00 Energy: 1.290e+(l()4 Btu/hr
Pump: P-101 Delta P: 485 3 psi
Adiabatic Efficiency ("o): 75.00 IJiergy: 5.5OOc+004 Btu/hr
Pump: P-102 Delta P: 3 40(1 psi
.Adiabatic Efficiency (%) 75.00 Energy: 484.6 Btu/hr
Recycles
Recycle: RCY-T and D Acceleration l>pe: Wegstein
Nl^MFRICAI. Iteration Tvpe Simultaneous
Recycle RCV-1 Acceleration T>pe: Wegstein
NCMI.RICAL Iteration Type: Nested
Adjusts
Adjust: ADJ-Tin2 Source Tor Target Value User Supplied
Solving Parameters Target Value: 1300 F
Adjust: ADJ-Tin3 Source for Target Value: User Supplied

Adjust: ADJ-TinI Source for Target Value: User Supplied

75
The following is the reactor Section 1 information in the modified HDA process.
1320
1300
1280
0) 1260
3
«->
ra 1240
a>
Q. 1220
E
0) 1200
1180
1160
50 100 150 200 250
Reactor length, ft
Figure D. 1: Temperature profile of Reactor 1 in the modified HDA process
3.OOE-01
SI
2.50E-01
Ie/ft3-
2.00E-01
F 1.50E-01
Reactior 1 Rate, Ib
1.OOE-01 Reaction-1
Reactions-2&3
5.00E-02
O.OOE+00
-5.00E-02
-1.00E-01
50 100 150 200 250
Reactor length, ft
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 -•—Toluene
o
••g 5.OOE-01 -•— Hydrogen
ra
u. -5r- Benzene
o> 4.OOE-01 ->^-Methane
o
-*-Diphenyl
3.OOE-01
50 100 150 200 250

Reactor Length, ft
Figure D.3: Component mole fraction in Reactor 1 ofthe modified HDA process
77
1320
1300 - - r- ' h -
1
u. 1280
o
^ 1260 1
re
g. 1240
E
1
^^
•- 1220
j
- - - . J — .
1200 !
1 1
1180
100 200 300 400 500 600 700 800 900
Reactor length, ft
Figure D.4: Temperature profile of Reactor 2 in the modified HDA process
2.50E-01
ole /ft -hr
2.OOE-01
CO
1.50E-01
E Reaction-1
.o
o 1.OOE-01 Reactions-2&3
*.»
ra
CH
c 5.00E-02
o
'*•>
u
0) O.OOE+00
a:
-5.00E-02
200 400 600 800 1000
Reactor length, ft
Figure D.5: Reaction rates in Reactor 2 ofthe modified HDA process
78
6.00E-t-02
500E+02
4.00E-I-02
c -•—Toluene
o
o -m— Hydrogen
re
3.00E+02 -&— Benzene
0)
O -^^—Methane
-^K—Diphenyl
2.00E-t-02 c.:.X-X-**-XHX—X—X—X
1,00E-t-02
O.OOE-^00
0 200 400 600 800 1000
Reactor Length, ft
Figure D.6: Component mole fracfion in Reactor 2 ofthe modified HDA process
79
1310
1300 .. „ 4 . ..... :
1290
Ll.
o 1280 jAr^ —
3
™ 1270
0}
E 1260
a>
1250 -- . : --
Jf
1240 ---'- i- ' -
1230
D 100 200 300 400 500
Reactor length. ft
Figure D.7: Temperature profile of Reactor 3 in the modified HDA process
2.50E-01
k.
s. 2.OOE-01
« Reaction-1
V
o Reactions-2&3
E 1.50E-01
a
<S
* j
CC 1.OOE-01
c
o
+J
o
ro 500E-02
CC
^^S^«^^*if4waB^
O.OOE+00
100 200 300 400 500
Reactor length, ft
Figure D.8: Reacfion rates in Reactor 3 ofthe modified HDA process
80
5.00E+02
4,50E+02
4.00E+02
S-H-a-HIHl-B
3.50E-I-02
c -•—Toluene
ictio
3.00E-t-02
x-)<-^^-x -«— Hydrogen
^ - ^ - -Jk-Tftr—A—*r~A—A,
u. 2.50E+02 -?:— Benzene
0)
2.00E+02 -^<—Methane
Mo
-*-Diphenyl
1.50E+02
1.00E+02
5.00E+01
O.OOE+00
100 200 300 400 500
Reactor Length, ft
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
Equipment Label* Equipment Bare Module

Cost** Cost***
1 Feed Pump P-101 $ 20,432 $ 67,628
- Heat Exchanger L-lOO $ 41,833 $ 286,547
1
Furnace Furnace $ 109,961 $ 415,655
4 Reactors PFR-lOO, PFR-101,
PFR-102
$ 195,000 S 220,000
5 Cooler E-103 $ 37,584 $ 130,915
6 Separator \-100 $ 16,931 $ 95.623
7 Product Column T-IOO $ 31,542 s 133,107
8 Recycle Pump P-100 $ 11,920 $ 30,454
9 Separator V-102 $ 12,129 $ 37,479
10 Separator V-IOI $ 2,300 $ 7,107
11 Heat Exchanger E-IO.S $ 13,152 $ 45.811
i: Heat Exchanger E-106 $ 8,860 s 30,861
1.3 Heater E-101 Included in Furnace
14 Heater E-102 Included in Furnace
i,> Cooler K-l(14 $ 16,843 $ 55,581
for Product t olumn T-
16 Reboiler 100 $ 16,112 s 53,169
for Product Column T-

17 Condenser 100 $ 21,066 $ 65,094
for Product C olumn T-
18 Reflux Pump 100 $ 9,538 s 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 C A P C O S r [24])
Chemical Hngineering Plant Cost Index (CEPCl) = ^Ri

Total Purchased Equipment Cost = $ 623,000
Total Bare Module Cost (CS and 0 barg) of Plant = $ 1.381,000
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
HEAT EXCHANGERS
Heat Exchanger, E-101
Area (m2) =696.7728 Equipment Cost = $41,833
Material of Construction =SS SS Bare Module Cost = $ 286,547
Heat E.xchanger, E-102 Shell Side Pressure (barg) =1
Kettle Reboiler Area (m2) =50 Equipment Cost = $ 16,112
Material of Construction =CS'CS Bare Module Cost = $ 53,169
FIRED HEATERS
Heater. H-l01 Tube Material of Construction=SS
Non-Reactive Fired Heater Equipment Cost = $ 209,451
Duty (kWj =984 Bare Module Cost = $ 791,724
Tube Pressure (barg) =200 barg
PUMPS
Pump, P-IOI Suction Pressure (barg) = 1
Material of Construction = Cast Equipment Cost = $ 20.432
Iron Power (kW)= 16.23 Bare Module Cost = $ 67,628
Material of Construction •• Cast Iron Equipment Cost = $ 1 1,920
Power (kW) = 3,81 Bare Module Cost = $ 39,454
Material of Construction = Cast Iron Equipment Cost = $ 6,928
Power (kW) = 0.75 Bare Module Cost = $ 22,930
Material of Construction = Cast Iron Equipment Cost = $ 9,538
Power (kW) = 2 Bare Module Cost = $31,570
83
TOWERS
lower, T-101 Number of Trays =20
Tower Material of Construction= CS Tray Material of Construction= CS
Diameter (m) =1.5 Vessel Cost = $31,542
Height/Length (m) =10 Internals Cost = $ 0
Pressure (barg) =1,5 Bare Module Cost = $ 133,107
VESSELS
Process Vessel, V-101 Height/Length (in) = 4
Vessel Orientation = Horizontal Equipment Cost = $ 16,931
Diameter (m) = 2.5 Bare Module Cost = $ 95,623
Diameter (m) = 2 Bare Module Cost = $ 37,479
Diameter (m) = 0.6 Bare Module Cost = $ 7,107
Process Vessel, V-104 Height Length (m)= 10
Diameter (m) = 2 Bare Module Cost = $ 65,094
REACTOR
USER ADDED EQUIPMENT Bare Module Factor (actual)= 1.12
User Added Equipment - 10 in Pipe Purchased Equipment Cost = $ 195,000
Bare Module Factor (CS -*- 0 barg)= Bare Module Cost = $ 220,000
Table D.4: Operating cost summary for the moditied HDA process
BTU/hr Dollars/hr*
Electrical power:
P-100 1.29E-^04 0.15
P-101 5,50E-H04 0.64
P-102 4.85E-H02 0,01
Fuel (Oil or Gas):
E-101 5.7IE-^05 2.29
E-102 l,26E+06 5.04
Furnace 6.62E-^05 2.65
Cooling water:
E-103 ^ 7.70E+06 0.04
E-104 6.39E-^04 0.04
T-UlO Condenser 1.25E-H07 6.77
Steam
T-100 Rebolier I.4IE+07 242.36
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 itfiêelyavaUable 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

HDA Process PDF

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

HDA Process PDF

Caricato da

Copyright:

Formati disponibili

AN EXAMINATION OF MODIFIED HIERARCHICAL DESIGN

STRUCTURE FOR CHEMICAL PROCESSES

STANISLAV VALERIEVICH EMETS, B.S.

Submitted to the Graduate Faculty

Chairper/on of the Committee

Dean of the Graduate School

me to accomplish this project.

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

chemical engineering at Texas Tech Universitx.

support during my work on the Master of Science degree.

1 OBJECTIVES AND MOTIVATION 1

2 CONVENTIONAL HIERARCHICAL DESIGN STRUCTURE

AND HDA PROCESS 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

4.1 Economic Potential and Profit Rate 26

4.2 Capital Cost Investment 28

4.3 Performance Comparison

A CALCULATION OF 11 lERMODYNAMIC AND KINETIC PARAMETERS 43

C THE CONVENTIONAL DESIGN OF HDA PROCESS 48

D THE MODIFIED DESIGN OF HDA PROCl'SS 65

examining several designs of hydrodealkylation (HDA) of toluene to benzene process (a

con\ entional design hierarchies.

obtained by conventional hierarchical design structure. Specifically, the plant designed

economic advantages are obtained mainly due to modifications in the reactor

configurations and the elimination ofthe gas recvcle stream.

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

the required plant-wide control stmcture. Also, it is recommended to examine the

2.1 Comparison of textbook examples using the HDA process 6

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

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

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

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