by STANISLAV VALERIEVICH EMETS, B.S. A THESIS IN CHEMICAL ENGINEERING Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE IN CHEMICAL ENGINEERING Approved Chairper/on of the Committee Accepted Dean of the Graduate School May. 2003 ACKNOWLEDGMENTS 1 am delighted to sa> that the outcome of this project vva.s very valuable and worth the effort spent. 1 thank my father, mother, and sister whose love and affection enabled me to accomplish this project. 1 would like to express m>- gratitude to Professor Uzi Mann, the chairman of my thesis committee, for his guidance, support, and influence. Not only has he taught me a lot technically, but also he was a true mentor. I also thank Professor Karlene Hoo for all the knowledge and skills that I learned from her, for all the suggestions that she has given me in completing my master's thesis successfully, and for serving on my committee. 1 also want to express my appreciation and thanks to the Phillips Petroleum Company for providing the fellowship that enabled me to pursue graduate studies in chemical engineering at Texas Tech Universitx. I would like to thank all my peers at Texas Tech for their encouragement and support during my work on the Master of Science degree. TABLE OF CONTENTS ACKNOWLEDGEMENTS ii ABSTRACT v LIST OF TABLES M, LIST OF FIGURES ix NOMENCLATURE xi ABBREVIATIONS xu CHAPTER 1 OBJECTIVES AND MOTIVATION 1 2 CONVENTIONAL HIERARCHICAL DESIGN STRUCTURE AND HDA PROCESS 4 2.1 Background 4 2.2 Design Objectives and Process Specifications 6 2.3 Process Conditions and Constraints 7 2.4 Thermodynamic and Kinetic Data 8 2.5 The Conventional HDA Design 13 3 THE MODIFIED HDA PROCESS 17 4 ANALYSIS: COMPARISON OF THE MODIFIED AND THE CONVENTIONAL DESIGNS 26 4.1 Economic Potential and Profit Rate 26 4.2 Capital Cost Investment 28 4.3 Performance Comparison Ul 5 CONCLUSIONS AND RECOMMENDATIONS 37 BIBLIOGRAPHY 40 APPENDIX A CALCULATION OF 11 lERMODYNAMIC AND KINETIC PARAMETERS 43 B ECONOMIC DATA 46 C THE CONVENTIONAL DESIGN OF HDA PROCESS 48 D THE MODIFIED DESIGN OF HDA PROCl'SS 65 ABSTRACT The goal of this work was to examine a modified hierarchical procedure for the conceptual design of chemical processes with chemical reactions. This was achieved h\ examining several designs of hydrodealkylation (HDA) of toluene to benzene process (a benchmark case in teaching chemical process design), using the modified and the con\ entional design hierarchies. The con\'entional design hierarchy as described by Douglas [1] has at least two drawbacks. First, the operation ofthe chemical reactor is not considered as a separate step ofthe design exercise, but rather as a part ofthe recycle structure. Second, the use of a recycle stream is pureh an economic decision that should be considered in the unit integration step, after the basic structure ofthe process is designed. Mann and Hoo [10] proposed a modified hierarchical design structure tor chemical processes that overcomes these drawbacks. Results of this study show that by applying the modified hierarchical design structure to design the HDA process, a more economical plant is designed than one obtained by conventional hierarchical design structure. Specifically, the plant designed by the modified hierarchy requires 70% lower capital investment (bare module cost) and provides an operating loss 50% smaller than that ofthe conventional design. These economic advantages are obtained mainly due to modifications in the reactor configurations and the elimination ofthe gas recvcle stream. These results indicate that the modified hierarchical design structure for chemical processes with chemical reactions proposed by Mann and Hoo [10] deserves further examination. The results indicate the importance of considering the design ofthe chemical reactor as a distinct step in the design exercise. The results also indicate that the implementation of a recycle stream should be assessed on the basis of economic considerations, rather than being an inherent part ofthe design procedure. It is recommended to continue the investigation ofthe modified hierarchical design structure and expand the study to include the dynamic behavior ofthe process and the required plant-wide control stmcture. Also, it is recommended to examine the application of the modified hierarchical design structure to ttther chemical processes with chemical reactions. VI LIST OF TABLES 2.1 Comparison of textbook examples using the HDA process 6 2.2 Kinetic data for Reaction 2 from Hougen and Watson 15] 10 2.3 Ke> process streams for the conventional HDA process 15 3.1 Key process streams for the modified HDA process 25 4.1 Major equipment costs ofthe HDA processes 29 4.2 Bare module costs of major units ofthe HDA processes 30 4.3 Equipment costs ofthe HDA process 31 4.4 Bare module costs of the HDA process 32 4.5 Total grass roots plant costs ofthe HDA process 33 4.6 Benefits ofthe modified design 33 4.7 Disadvantages ofthe modified design 33 4.8 Comparison ofthe reactor design based on coiTccted rate expressions 35 B. 1 Toluene and Benzene price information [27, 28] 47 B.2 Hydrogen and Methane fuel values information [1] 47 C. 1 Conditions and compositions for all material streams ofthe conventional HDA process 49 C.2 Parameters for equipment ofthe conventional HDA process 54 C.3 Process unit costs for the conventional HDA process 60 C.4 Operating cost summary for the conventional HDA process 64 D. 1 Conditions and compositions for all material streams ofthe modified HDA process 66 Vl l LIST OF TABLES (continued) D.2 Parameters for equipment ofthe modified HDA process 73 D.3 Process unit costs for the modified HDA process 82 D.4 Operating cost summary for the modified HDA process 85 Mi l LIST OF FIGURES 2.1 Plot of In ( k,v ) \ ersus 1/T 11 2.2 Fhe input/output structure of the conventional 11 DA process 14 2.3 The conventional HDA process 16 3.1 An "'ideal" input/output structure of HDA process 17 3.2 The input/output structure of the proposed modified HDA process 19 3.3 .A reactor with distributed side injection 20 3.4 Potential reactor configuration for the modified I IDA process 20 3.5 A plot of Hin/TLjn ratio versus reactor sections 22 3.6 The modified HDA process 24 C. 1 Temperature profile ofthe reactor in the conventional HDA process 58 C.2 Reaction rates in the reactor of the conventional HDA process 59 C.3 Component mole fraction in the reactor ofthe conventional HDA process 59 D. 1 Temperature profile of Reactor 1 in the modified HDA process 76 D.2 Reaction rates in Reactor 1 ofthe modified HDA process 76 D.3 Component mole fraction in Reactor 1 ofthe modified HDA process 77 D.4 Temperature profile of Reactor 2 in the modified HDA process 78 D.5 Reaction rates in Reactor 2 ofthe 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 D.8 Reaction rates in Reactor 3 ofthe modified HDA process 80 IX IST OF FIGURES (continued) D.9 Component mole fraction in Reactor 3 of the modified HDA process 81 NOMENCLATURE .A, reaction rate pre-exponential coefficient of i"' reaction, depend on reaction c , molar-based specific heat of species j , BTU/lbmole-K Eaj activation energy of i'^ reaction, energy/lbmole EP economic potential, $/hr Hf standard heat of formation of species j , BTU/lbmole .AHp, ( T) heat of reaction at temperature f, BTU/lbmole AH,, (298 K) heat of reaction at standard conditions (1 aim and 298 K). BTU/lbmole 1^2^' dimensionless reaction \elocity constant of Reaction 2 k| rate constant of i-th reaction L/D length-to-diameter OC operating costs. $/hr p partial pressure of species j . psia PR profit rate, $/lir R universal gas constant, cnergy/lbmole-R r reaction rate of i"' reaction, Ibmole/min-ft s stoichiometric coefficient of species j T temperature, depend on equation j . ^ inlet temperature, depend on equation X^^j outlet temperature, depend on equation XI ABBREVIATIONS B benzene CS D H carbon steel diphenyl hN'droiicn HDA the hydrodealkylation of toluene to benzene M methane P PFR SS TL pressure plug-flow reactor stainless steel toluene XII CHAP! ER 1 OBJECTIVES AND MOTIVATION The objective of this work is to investigate the effectiveness of a modified hierarchical structure for conceptual design of chemical processes involving chemical reactions. This is accomplished by examining (comparing) several designs ofthe hydrodealk\'lation (HDA) of toluene to benzene process, using the modified and the conventional design hierarchies. A design that yields a more economical plant (higher profit, lower investment, etc.) is considered superior. The conventional process design procedure consists of a hierarchical structure described by Douglas [1]. The main elements ofthe design procedure are: 1. Selection of batch or continuous operations, 2. Identification of an input/output structure, 3. Identify a recycle structure, 4. Identify a separation structure, 5. Consideration of heat integration. This hierarchical stmcture has at least two drawbacks. First, for process involving chemical reactions, the operation ofthe chemical reactor is not considered as a distinct step ofthe design exercise, but rather as a part ofthe recycle structure [1]. In most chemical processes with chemical reactions, the chemical reactor is the "heart" ofthe process, and its operation determines the conditions at which other units in the process operate [11]. Second, the use of a recycle stream is purely an economic decision, and should not be decided upon a priori, as implied from the current process design hierarchy. In this context, a "recycle" is defined as a fraction of a stream (at the limit, the entire stream) that is relocated, without modifying its composition to a point upstream in the process. An alternative to a recycle is to change the composition ofthe stream (by a separation unit) and then direct the modified (separated) streams either to storage or to points in the process. Of course, the advantage of a recycle is that it does not involve the additional separation step and its associated costs. However, the main disadvantage of a recycle is that if the stream contains some species that are not removed, they build-up in the process and this necessitates purging of a portion ofthe recycle stream, resulting in the loss of valuable components. Only when the cost of purging the valuable components is low. and the expense of recycling (e.g., compression) is not high, recycle is economical. Another disadvantage of recycle is that it complicates the dynamic (non- steady state) behavior ofthe process by adding interactions among the process variables. This makes the synthesis of a control system much more difficult. However, this impact is not considered in this work, which is limited to steady state design. A modified hierarchical structure for designing chemical processes with chemical reactions that addresses these drawbacks was recently proposed by Mann and Hoo [10]. It adds a distinct step of considering the design and operation of a chemical reactor to the design procedure, and it moves the consideration of recycle to the unit integration step. Hence, the main elements ofthe modified design hierarchy are: 1. Selection of batch or continuous operations, 2. Identification of an input/output structure. 3. Identify and select reactor subsystem, 4. Identify and select separation subsystem, 5. Considering unit integration to maximize profit: a. material rec>cle management, and b. heat integration. The purpose of this work is to examine whether the modified hierarchical structure for conceptual design of chemical processes provides a superior design than the con\ entional structure. The HDA process to produce benzene from toluene was selected, as an example to compare the two hierarchical structures because it is an instructional case in the pedagogy of chemical process design. The thesis is organized as follows. Chapter 2 provides a review ofthe conventional process design hierarch\. describes the HDA process, and provides the thermodynamic and kinetic data needed for the design. Chapter 3 describes the modified HDA process. Chapter 4 provides an economic comparison ofthe modified and the conventional HDA process. Chapter 5 pro\'ides a summary ofthe conclusions drawn from this study and a list of recoiumendations for future work. CHAPTER 2 CONVENTIONAL HIERARCHICAL DESKiN STRUCTURE AND HDA PROCESS 2.1 Background The design exercise has a major impact on the economics and the sustainability oi" chemical processes. Many decisions made during the design determine the economical performance ofthe plant, its effects on the environment, and its adaptability to changes in market conditions. By its nature, process design is done on the basis of incomplete information. Therefore, tlnding an efficient methodology for conceptual process design is important. In general, the design of chemical processes is divided into two distinct stages. First, the process is designed for steady-state operation to meet the specified production objectives and product purit\'. This stage leads to the formulation of a process flow sheet, which defines all the units in the process and their connectivity. Second, a control system is designed to maintain the specified operating conditions in spite of disturbances. The design ofthe control system and the selection ofthe control components are carried out after the flow sheet is completed, and these tasks are considered to be the doinain ofthe process control engineer. This work is limited to the first stage: steady-state design and the formulation of a process fiow sheet. The design exercise of chemical processes has been covered extensively in the literature, and its principles are taught in the senior year ofthe chemical engineering curriculum. While different textbooks provide different eiuphasis on various aspects of the design exercise [1, 2, 6, 11, 26], all of them follow the basic hierarchical structure de\ eloped b> Douglas [1]. Howexer. because ofthe limitations indicated in Chapter 1, it is useful to examine a modified design hierarchy to determine whether it may result in a superior process flow sheet; i.e., in a plant that is more economical. The h\drodealkylation (HDA) of toluene to benzene process has been used as an instructional case in teaching chemical process design, and is extensively covered in the literature [1-3, 6, 11-21]. In this process, hydrogen and toluene react to form benzene; methane is formed as a by-product ofthe reaction. At the reactor operating conditions, benzene also reacts to form diphenyl in a secondary reaction. The HDA process encompasses the follow ing common issues that appear in many chemical processes: 1. Constraints on the proportion ofthe reactants. Constraints on the reactor temperature. Implementation of recycle streams, 4. Application of heat integration. Table 2.1 provides a eoiuparison ofthe differences among several HDA flow sheets (designs). In the design ofthe HDA process coxered in the textbooks, the design ofthe chemical reactor is not considered in detail. In fact, in all of them, the size ofthe reactor is calculated assuming that the reactor is ideal plug-flow, and operates isothermally (temperature varies narrowly from 1,150 to 1,260'T). Also, in all cases, the reactor is designed for 75% conxersion of toluene to obtain a pre-specilied yield of benzene. 1 J . Table 2.1: Comparison of textbook examples using the HDA process Textbook .Author Douglas |1] 1 urton et al. [6] Smith [11] Siederetal. |2] Luyben et al. [3] Number of chemical reactions considered 1 1 1 T 1 Number of distillation columns -> 1 .1 Discharge of diphenyl as a pollutant Considered Not considered C onsidered Considered Considered Recycle of diphenyl to the reactor Considered Not considered Not considered Not considered Not considered 2.2 Design Objectives and Process Specifications The design task at hand is to design a chemical process to produce benzene at a rate of 265 Ibmole/hr with a product (benzene) purity of 0.997. Two streams are assumed to be aA ailable for the process: a gas stream containing (in mole %) 95% hydrogen and 5o methane, at a pressure of 550 psia and a temperature of lOO'T; and a liquid stream of toluene, at ambient temperature and atmospheric pressure. To achiexe the specified objectives, a process based on hydrodealkylation (HDA) of toluene to benzene is considered. The following non-catalytic, gas-phase chemical reactions take place in the process: Reaction 1: C, H, +Hj _ C H + CH4 Reaction 2 and 3: 2CH ^ C , . H , + H, That is, hydrogen and toluene react to form benzene and methane in Reaction 1, and diphenyl is formed in the secondary reaction. Note that the secondary reaction is reversible reaction, and the forward reaction is denoted as Reaction 2 and the reverse reaction is denoted as Reaction 3. For simplicity, in the remainder ofthe thesis, benzene (CftHft) will be denoted by B, toluene (CvHx) by TL, hydrogen (H2) by H, methane (CH4) by M, and diphenyl (C12H10) by D. 2.3 Process Conditions and Constraints Experimental kinetic studies indicate that the following constraints should be imposed on the reactor operating conditions [1-3, 6, 11]: 1. To achieve satisfactory reaction rate, the inlet reactor temperature should be maintained at 1.150'T or higher. 2. The reactor temperature must not exceed 1,300"F to prevent a significant amount of hydrocracking. 3. The proportion of hydrogen-to-toluene at the inlet ofthe reactor should be at least five to reduce coking. 4. The outlet stream from the reactor should be quenched. In addition, the reactor pressure cited in the literature is 500 psia [1, 31, and it is assumed that the reactor is operated at this pressure. In principal, the reactor pressure can be optimized to maximize profit, but since the objective of this work is to compare the modified design procedure to the conventional one, the stated reactor operating pressure is used. 2.4 fhermodynamic and Kinetic Data fo carrx out the design ofthe HDA process, thermodynamic and kinetic data are needed. A literature survey indicates an inconsistency in the data used in the conventional design [3]. Thus, these inconsistencies are first reconciled in order to make the comparison ofthe modified design procedure meaningful. The thermodynamic and kinetic data used by Lux ben et al. [3] and other inxestigators [1,6] are inconsistent because the activation energy (Ea) of Reaction 2 was taken to be equal to the activation energy of Reaction 3, its reverse reaction, thus implxing that the heat of reaction of Reaction 2, AH^^, is zero. However, the heat of reaction of Reaction 2 is not zero, as reported by Hougen and Watson [5]. Also, the calculation ofthe heat of Reaction 2 from the heat of formation ofthe .species, based on the thermodynamic database of H\SYS.PLANT 2.2 |25], indicates that AH^^ is not zero. To resolve this inconsistency and to verify all thermodynamic data, the species heat of formations [7] and their specific heat capacities [8] are used to calculate the heats of reaction of Reactions 1 and 2. The heat of reaction at standard conditions (1 atm and 298 K) is obtained from species heat of formation bx (see. for example. Smith et al. [29|) AH",(298K) = Xs , H' ; , , (2-1) J where s is the stoichiometric coefficient of species j in the reaction. At temperature T, the heat of reaction is. AH, (T)=AHi ; (298K)+ j X^ i ^ P ^ T , (2-2) where c,,^ is the molar-based specific heat of species j . Ba.sed on published themiodynamic data [7, 8], the calculated heats of reaction of Reactions 1 and 2 are (see detailed calculation in Appendix A): For Reaction 1 AH; ; (298 K) =-1. 803 10' BTU/lbmole AHR (l 150 F)=-2.096-10"* BTU/lbmole For Reaction 2 AH',; (298 K) = 6.9X4-10' BTU/lbmole AH,, (1 150F) = 1.118-10' BTU/lbmole. Note that AH,, is consistent xvith the value used bx Luyben et al. [3] and others. Hoxxex er. AH at 1.150"F is 1.118-10"* BTU/lbmole, and not zero as assumed. The reaction rate expressions for the three chemical reactions are provided by [3]: r, = A, exp(-l':a|/RT)pT. p, , "' (2-3) r, = A. exp(-Ea2/RT) p^' (2-4) r^ = A3 e.xp(-EayRT) p p,, (2-5) where r|. ri and r3 are the reaction rates expressed in lbmole/(min-fr );P| (j = TL, H, B, D) is the partial pressure (psia) of species j ; Ai, A2, and A; are the reaction rate pre- exponential coefficients for Reaction 1, 2 and 3, respectively; Eai, Ea^, and Ea3 are the respective activation energies; T is the absolute temperature; and R is the universal gas constant. Since the heat of reaction of Reaction 2 is not zero, the rate expressions of Reactions 2 and 3 should be reconciled to account for the different activation energies. To do so, the kinetic data of Reaction 2, reported by Hougen and Watson [5], are used (see Table 2.2) to obtain the activation energx'. The reported reaction rate velocity Table 2.2: Kinetic data for Reaction 2 from Hougen and Watson [5] Temperature, K 644.26 699.82 755.37 Dimensionless reaction velocity constant, k^v 0.15 1.00 5.00 810.93 ' 20.00 866.48 922.04 977.59 1,033.15 70.00 200.00 500.00 1,000.00 constants at different temperatures are plotted using the Arrhenius equation. ln(k,A' ) = La, RT -I- constant (2-6) where k^v is the dimensionless reaction velocity constant of Reaction 2. Even though Hougen and Watson [5] use the dimensionless reaction velocity constant rather than the absolute value ofthe reaction rate constant, the determination ofthe actixation energx of Reaction 2 is still possible. Using the data from Table 2.2. Figure 2.1 is generated. The straight line has a slope equal to -Eaj/R. From the slope ofthe curve, the value of Ea./R is 15,362 K. Now that the value of Ea2/R is known, using the relationship between the heat of reaction and the activation energies ofthe forward and backward reactions, AH,, =I-;a . , , - Ea_, (2-7) 10 Figure 2.1: Plot of In ( k, r ) versus 1/T Ea3/R ofthe reverse reaction can be calculated as follows: Ea, - Ea, = AH (2-8) Ea, Ea, AH,,^ R R R (2-9) Ea, Ea, AH, R R R ' - - " Appendix A provides more details on how the value of EaVR is determined. The calculated value of Ea3/R is 12.237 K. Since the calculated values Ea2/R and Ea3/R are different than those in the rate expressions used in the literature, consistent rate expressions should be used in both cases. In order to match the adjusted reaction rates of Reactions 2 and 3 (with different Lai and Lai) with the reaction rates used in the literature, each expression was required to provide the same value at 1,150'T (the reactor inlet temperature). 11 For Reaction 2. A, l.ahuMal^'-'^P ^^:(;Kl| ustcci)/R ' 894.26 = 5.987-lO'e.xpl For Reaction 3. /\ Md,MC,l,eXP 894.26 2.553 lO'exp Ea, / R 894.26 f E a , / R ^ 894.26 (2- (2-12) Soix ing these expressions, the following xalues arc obtained (see Appendix A): Ibmole A:,, =0.62717- A,d,s,ed,-0.08124- min - It - psia" Ibmole min-ft' -psia" Using these calculated x alues. the adjusted reaction rate expressions are: ( 2.5616-10' ^ r, = 3.6858-lO' exp T PTPH r, =0.62717 exp 1.5362-10 T 4 X r, =0.08124 exp ^ 1.2237-10"'^ T Pn" PD PI (2-131 ( 2- 1 4 ) (2-15) where ri, r2, and r3 are in lbmole/(min-ft'). and T is in degrees K. and p, is in psia. These corrected rate expressions are used, in this study, to design the reactor ofthe HDA process. 12 2.5 The Conventional 1 IDA Design The conx entional HDA process is designed following the design hierarchy presented bx Douglas [1] and outlined in Chapter 1. This design is used as the base case to xvhich the modified HDA process is compared. .A schematic ofthe input/output structure ofthe conventional HDA process is shoxvn in Figure 2.2. The process consists of reactor and separation systems. The conx entional design was carried out under the assumption that the conxersion of toluene in the reactor is 75%). Stoichiometrx indicates that Reaction 1 requires a 1-to-l proportion of toluene and hydrogen. However, as indicated, the chemistry necessitates a 5-to-l ratio of toluene and hydrogen at the inlet ofthe reactor to reduce carbonization of the toluene. Therefore, for each mole of benzene formed, five moles of hydrogen should be fed to the reactor. Further, since the conversion of toluene is only 75%, for each mole of unconverted toluene, fixe moles of hydrogen should be fed into the reactor. The excess amount of hydrogen (aboxe the stoichiometric amount) acts as an inert, and taxes the reactor operation by diluting the reactants. It also advocates recycling the unconverted hxdrogen from the separator to the reactor [1]. Note that the ct)nventional design is based on constructing a separating unit, xvhich remox es the gaseous species from the heavier components but does not separate methane from hydrogen. The effluent ofthe reactor contains methane (which is formed as a by-product), and since the methane is not removed, its level grows in the recycle stream and in the reactor. Also, recxcling methane increases the operating cost. Presence of methane at the reactor inlet reduces the concentration of reactants (toluene and benzene) throughout the reactor. To avoid 13 H M Tl ^ Recycle of H and M (gas-phase) r i k Reactor System Recycle Separator System af TL (liquid-phase) ^ H M ^ n Figure 2.2: The input/output structure ofthe conventional HDA process methane build-up, a portion ofthe gas recxcle needs to be purged. Note that the level of methane in the recycle loop is a design decision based on economic considerations (affects the amount of hydrogen purged) and safety considerations. The larger the flow rate ofthe purge stream, a large amount of hydrogen is lost, but lower levels of methane are recycled. The conventional HDA process is designed such that the level of methane at the reactor inlet is around 54 mole%. This results in a hydrogen loss at a rate of about 636 Ibmole/hr in the purge stream. The flow diagram ofthe conventional HDA process is shown in Figure 2.3. The design ofthe conventional HDA process (see Appendix C) is accomplished using HYSYS.PLANT 2.2 [22] and the UNIQUAC thermodynamic property package. The design follows the information provided bx Douglas 11]. Luyben et al. | 3], and the 14 coiTected (modified) rate expressions derived in Section 2.4. The information about key process streams for the conventional HDA process is shown in fable 2.3. Table 2.3: Kex process streams for the conventional HDA process Fl ow rat e, Ibmole hr Temper at ur e, "F Mol e fraction H M B TL D Fresh Toluene Stream 285. 9 86 0. 0000 0. 0000 0. 0000 1.0000 0. 0000 Fresh Hydrogen Stream 4%. 4 86 0. 9700 0. 0300 0. 0000 (1 0000 0. 0000 Reactor Inlet Stream 4 382.5 1 150 0.42' ) 1 0.4800 0.0053 0. 0856 0.0000 Reactor Effluent Stream 4 382 5 1 263 0.3644 0.5463 0.0685 0.01^)3 0.0015 Purge Stream 636. 8 115 0 391)2 0.5937 0.0065 0.0006 0.0000 Product Stream (Benzene) 265 211 0.0000 0.0000 0.9997 0.0003 0.0000 By- Product Stream (Diphenyl) 6.8 559 0.0000 0.0000 0.0000 0.0003 0.9997 Gas Recycle Stream 3 519.2 115 0.3992 0.5937 0.0065 0.0006 0.0000 Toluene Recycle Stream 82.1 272 0.0000 0.0000 0. 0006 0.9994 0.0000 15 CHAPTER 3 THE MODIFIED HDA PROCESS This chapter describes the design ofthe modified HDA process using the modified hierarchy proposed bx' Mann and Hoo [10]. 1 he main elements ofthe modified hierarchy are: 1. Selection of batch or continuous operations, 2. Identification of an input/output structure, 3. Identify and select reactor subsystem. 4. Identify and select separation subsystem, 5 Considering unit integration to maximize profit: a. material recycle management. b. heat integration. The design goal is the same as that ofthe conventional HDA process: to produce 265 Ibmole/hr of benzene with a purity of 0.997. First, an "ideal"" input/output structure, shown in Figure 3.1, is considered for the production of benzene only (without the second, undesirable reaction). This represents the ideal case where all the raw materials Toluene Hydrogen HDA Process -> Benzene Figure 3.1: An "ideal" input/output structure of HDA process 17 (toluene and hydrogen) are completely converted to produce the desired product (benzene) xvithout formation of any by-products (methane and diphenyl). However, the HDA process involxes three simultaneous chemical reactions with the primary (desirable) reaction generating methane in addition to the benzene and a secondary reaction generating diphenx I. As a result, decisions have to be made on what to do with the diphenyl and methane, and the unconverted toluene and hydrogen. Further, from enxironmental consideration, it is desirable not to discharge the diphenyl and unconxerted toluene (liquid products) from the process. Thus, the fust modification proposed is to recycle the diphenyl and unconx erted toluene to the reactor inlet. Note that the undesirable reaction (Reaction 2) is rexersible, and the diphenyl can be converted to benzene if its concentration in the reactor increases. Hence, the diphenyl can be recycled to extinction as pointed out bx' Douglas [1]. However, although the benefits of recycling the diphenyl have been recognized in the literature, the standard design case ofthe HDA process does not incorporate diphenyl recxcle. The second proposed modification to the conx entional process involves the design ofthe chemical reactor such that the amount of excess hydrogen fed to the reactor is smaller xvithout \iolating the hydrogen/toluene ratio of 5:1 at any point in the reactor. .Assuming this is achievable, the flow rate of recycled hydrogen can be substantiallx reduced, and consequently, the problem of methane build-up is mitigated. As a first design alternative, a process xvith no gas recycle, shown schematically in Figure 3.2, is considered. Comparing this modified process to the conxentional one (Figure 2.2), note that no diphenyl is being discharged from the process, eliminating potential 18 enxironmemal problems. .Also, the elimination ofthe gas recycle stream provides potemial economic advantage in eliminating a large component ofthe capital (compressor) and reducing the operating cost ofthe process. cost II M Tl i i Reactor System Separator System Recxcle of TL and D (liquid-phase) ^ H M ^ rt Figure 3.2: The input/output structure ofthe proposed modified HDA process In order to implement the HDA process shown schematically in Figure 3.2. it is necessarx to identify a reactor configuration that does not restilt in the discharge of a large amount of unconverted hydrogen. Traditionallx. the selection ofthe reactor configuration has been done solely on the basis of maximizing the yield ofthe desirable product (see, for example. Smith [11], Douglas [1], Levenspiel [25]). However, in general, maximizing the yield does not necessarily correspond to maximizing profitability. As indicated in Chapter 2, the dominating factor that affects the economics ofthe HDA process is the large amount of hydrogen that should be fed (and recycled) to the reactor. The key challenge in designing the reactor is: 19 Maintaining a - > 5 ratio imposed by the chemistry at each point in the reactor, while minimizing the excess amount of hydrogen fed. The modified reactor configuration is based on injecting the toluene along the reactor as it is being consumed, rather than feeding the toluene at the reactor inlet (see Figure 3.3). This is potentially achievable since Reaction 1 is exothermic, and complete conversion of toluene is possible in excess hydrogen. To assess this reactor TL,n Figure 3.3: A reactor with distributed side injection configuration, consider first that the reactor is divided into n sections, and the same amount of toluene is injected into each section, TLm/n, as shown in Figure 3.4. TL,n _ Hj n TL,n/n Section n=l TL,/n Section 2 n=2 TL,/n Section n Figure 3.4: Potential reactor configuration for the modified HDA process To estimate the required total flow rate ofthe hxdrogen into the reactor (H;,,). consider first the ideal ease, xx hen only Reaction 1 occurs. It is also assumed that the toluene, which is the limiting reactant, is completely converted in each section ofthe reactor. From stoichiometrx, the molar flow rate of hydrogen at the inlet ofthe n"^ section is H =H, TL,. (3-1 V n The inlet to the n-th section is the point in the reactor with the lowest H/TL ratio. The imposed hydrogen-to-toluene ratio at the inlet ofthe n"' section ofthe reactor is (n-\\ H V n j TL TL n TL, >5 (3-2) From Eq.(3-2). Hm'TLin relationship is derived H, 4 + n ^ ^ (3-3) Note that as n> co . Hj|,/TLjn ratio goes to 1, which is the stoichiometric proportion of hxdrogen and toluene in Reaction 1. Therefore, in principle, hydrogen and toluene can be fed to the reactor in stoichiometric propoilions if a reactor xxith continuous side injection is used (see Figure 3.3). Using Eq.(3-3). a plot of H,/TLin ratio versus the number of reactor sections is constructed and shown in Figure 3.5. The figure shows how the required total hydrogen feed can be reduced and how many reactor sections are needed to achieve it. Note that the largest reduction in the Hin/TLi,, ratio occurs when the reactor is divided into two or three sections. When only three sections are used, the Hin/TLin ratio is reduced bx more than 50%. 5 7 9 11 n (number of reactor sections) 13 15 Figure 3.5: A plot of Hin/TL,,, ratio versus reactor sections In designing the modified HDA process, it was assumed that each section ofthe reactor is operated adiabatieally. and is described by a plug-flow reactor (PFR) model [4|. From practical engineering perspectixe. this model holds for fully developed turbulent flows XXhen the length-to-diameter (L/D) proportion is greater than 20 [4]. The inlet temperature of each section is maintained at 1,150''F, and at any point in each section, the temperature is not allowed to exceed 1,300'T, the highest allowable temperature imposed by the chemistrx. Note that these are steady state operating conditions, but do not consider dynamic (non-steady state) variation ofthe temperature. 11 The reactor is designed for the three simultaneous reactions, and various level of diphenyl in the reactor inlet. The different cases are assessed according to the following criteria: 1. Smallest overall reactor size that provides complete conversion of toluene in each section ofthe reactor. 2. Keep the production of diphenxi at a loxv level. 3 Keep the production of benzene at a high level. 4. Operate the reactor at temperatures close to 1.300"F. The reactor design equations were solved using HYSYS.PLANT 2.2 [22] and the solutions checked by using the numerical method software LliQ" [23]. Reactors with txxo, three and four sections are considered. Studies show that a reactor with three sections provides a configuration with the smallest oxerall reactor xolume, and loxx diphenyl flow rate. After the reactor is designed, it is incorporated into the design ofthe HDA process using H\'SYS.PLANT 2.2 [22]. Details ofthe design are provided in Appendix D. The HDA process xx ith the modified reactor system is shown in Figure 3.6. and the kex' process stream information is provided in Table 3.1. (U o X -a -5 OJ 3 OB 24 Table 3.1: Kex process streams for the modified HDA process Flow rate, Ibmole/hr Temperature, "F Mole fi-action H M B TL D Fresh Toluene Stream 269 86 0.0000 0.0000 0.0000 1.0000 0.0000 Fresh Hydrogen Stream 665.6 86 0.9700 0.0300 0.0000 0.0000 0.0000 Total Reactor System inlet 976.8 1175 0.6609 0 0204 0.0000 0.2853 (1.0333 Reactor Effluent Stream 976.^) 1300 0.3856 0.2')5S 0.2753 0.0100 0.0333 Purge Stream 656.3 80 0.5723 0 4240 0.0037 0.0000 0.0000 Product Stream (Benzene) 265.1 167 0.0000 0.0002 0.^)')^)7 0.0001 0.0000 Toluene and Diphenyl Recycle Stream 42.2 1168 0.0000 0.0000 0.0001 0 2293 0.7706 25 CHAPTER 4 ANALYSIS: COMPARISON OF THE MODIFIED AND THE CONVENTIONAL DESIGNS 4.1 Economic Potential and Profit Rate In general, ex erx design of a chemical process is assessed on the basis ofthe economic feasibilitx ofthe final process. Hence, to compare the modified and conventional design procedures, an economic assessment is carried out for each, and then compared. For each case, an economic potential is done in each stage ofthe design exercise. Since the prices of chemical species vary, to determine the economic potential, fixed X alues are assigned to each reactant and product. The prices are taken from Chemical Marketing Reporter for December 2001 (see Appendix B). Values ofthe hydrogen and methane in the purge stream are taken as their heating values, as was done by Douglas [1]. The first step in evaluating the economic feasibilitx of a chemical process is to conduct a simplified economic potential (EP) - how much profit can the process generate. For the input/output structure, the economic potential is defined by all products Product flow rate, Ibmole/hr Product value, $/lbmole z all law inalenais Reactant 1 flow rate, Ibmole/lir Reactant "i value, $/lbmole^ (4- where EP indicates the potential profit the process can generate, expressed in $/hr. The comparison ofthe modified and conventional HDA designs begins with an evaluation of 26 their economic potential using the input/output structures (Figures 2.2 and 3.2. respectivelx). the associated species flow rates (see Appendices C and D). and the species prices (see Appendix B). For the input/omput structure ofthe HDA process, the economic potential is given bv. EP = Benzene V < ^ Value of ^ Production Rate, Ibmole/hr ^Diphenyl ^ Flow Rate, Ibmole/hr, Benzene, $/lbmole V ^ Value of ^ Diphenyl, $/lbmole J + Purge Floxv Rate, Ibmole/hr ^ Value of ^ Purge, $/lbmole ^Toluene ^ Feed Rate, Ibmole/hr ^ Value of ^ Toluene, $/lbmole '^ Hydrogen y Value of ^ (4-2) / Feed Rate, Ibmole/hr ) \ Hydrogen Feed, $/lbmole Substituting values ofthe conventional design (Figure 2.2) into Eq.(4-2) gives an EP of - 400 $/hr. Note that the EP is negative, indicating that the process is not economically feasible at the prevailing prices ofthe products and raw materials. It should be mentioned that, from an economic perspective, when the EP is negative, an engineer should look for other design alternatives to achieve the specified process design objectives. Hoxxexer. the purpose of this xxork is to compare the conventional HDA design with the modified design, and this can be done ex en though the economic potential is negative. Substituting values for the modified design (Figure 3.2) into Eq.(4-2) gives an EP of - 482 S/lrr. Hence, based on input/output stmcture alone, the modified design is slightly less economical than the conventional design. 27 The next level of an economic assessmem incorporates the operating cost (OC). The profit rate (PR) of a process is defined bx PR($/hr)= EP($/hr)-OC($/hr). (4,3, The operating cost consists ofthe expenses related to operating the process and includes utility, labor, and maintenance [6]. In the early stages of a design exercise, only the main utility costs are considered. A more accurate PR is calculated as the process flow sheet is dexeloped and the operating costs ofthe individual unit operations are defined. Considering the conxemional HDA process (Figure 2.3). the utilitx cost (power and energx requirements), calculated by HYSYS.PLANT 2.2 [22] and presented in Appendix C. is 1,040 $/hr. Hence, using Eq.(4-3). the calculated profit rate for the conventional HDA process is -1.440 $/hr. For the modified HDA process (Figure 3.6). the utility cost, as calculated by HYSYS.PLANT2.2 [22] and presented in Appendix D, is 260 $/hr. Hence, the profit rate ofthe modified HDA process is -742 $/hr. Note, the loss rate ofthe modified process is about 50% smaller than the loss rate ofthe conventional process. 4.2 Capital Cost Investment The next element in assessing the economic viability of a chemical process is to estimate the cost of construction. The capital cost is used to determine the return on investment and is amortized to determine a realistic profit rate. The equipment cost is calculated using a common procedure, described, for example, by Turton et al. [6]. The equipment cost is determined for a tabulated unit of known size, and then, the cost is 28 adjusted bx- a scaling factor. Also, the tabulated values, which are given for a specified date, are corrected to the cuiTent cost using a cost index. Different equipment costs are defined and used in the literature, fhe first one is the cost of manufacturing the equipment at the manufacturer location. Table 4.1 provides a comparison ofthe major equipment costs for the txxo designs. Note that the cost ofthe main units for the modified design is about 4()"(i lower than that ofthe conventional design. Table 4.1: Major equipment costs ofthe HDA processes Equipment 1 Heat exchanger 2 Furnace "> Reactor sx stem 4 5 Separation sx stem Recycle coinpressor Total Modified Design $41,833 $ 109,961 $ 195,000 $ 164,045 N/A $ 510,839 Conventional Design $ 167,332 $209,451 $ 51.490 $ 320.240 $ 83,585 $ 832,098 The next equipment cost is called the "bare module cost" [6], indicating the cost ofthe installed unit in the plant. It usually refers to the cost of making small-to moderate expansions or alterations to an existing facilitx. Bare module cost includes both direct and indirect costs. The direct cost consists of equipment (f o.b.) cost, materials required for installation, labor to install equipment and material. The indirect cost includes freight, insurance, taxes, construction overhead, and contractor engineering expenses. Table 4.2 shows the comparison ofthe major bare module costs betxveen the txvo HDA process designs. Note that the total bare module cost ofthe modified process is about 65%) lower than that ofthe conventional process. 29 Table 4.2; Bare module costs of major units ofthe HDA processes 1 "> 3 4 5 Eciuipment Heat exchanger Furnace Reactor sx stem Separation system Recycle compressor Total Modified Design $ 286,547 $415,655 $ 220,000 $ 609,645 N/A S 1,531,847 (-'onventional Design $ 1,146.188 $791,724 $912,985 $ 1,399,198 $226,619 $4,476,714 Tables 4.3 and 4.4 prox ide a comparison ofthe detailed equipment costs and bare module costs for the txxo designs. Note that \xhen considering all the elements ofthe HDA process, the total bare module cost ofthe modified design is about 70% lower than that ofthe conventional design. Another cost estimate commonly used is the grass roots plant cost [6]. It refers to the cost of a new facilitx, where the construction starts on essentially undeveloped land (a grass field). Table 4.5 shows the total grass roots plant costs comparison for the modified and the conventional HDA processes. Note that if the HDA process is constructed, the cost ofthe modified process is about 57% ofthe cost of a conventional plant. Table 4.3: Equipment costs ofthe HDA process 1 1 2 3 4 5 6 7 Equipment -^eed Pump -leat Exchanger -urn ace Reactor(s) Cooler Separator Stabilizer Column 8 iProduct Column 9 Recxcle Column 10 IRecxcle Pump 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Recycle Compressor Separator Separator Heat Exchanger Heat Exchanger Heater Heater Cooler Reboiler Condenser Reflux Pump Reboiler Condenser Reflux Pump Reboiler Condenser Reflux Pump Total Modified Design Label (Figure 3.6) P-101 E-lOO Furnace PFR-100, PFR-101, PFR-102 E-103 V-100 N/A T-1 GO N/A P-100 N/A V-102 V-101 E-105 E-106 E-101 E-102 E-104 For Column T-100 For Column T-100 For Column T-100 N/A N/A N/A N/A N/A N/A Cost $ 20.432 $41,833 $ 109,961 $ 195,000 $37,584 $ 16,931 N/A $31,542 N/A $ 11.920 N/A $ 12.129 $ 2,300 $ 13,152 $ 8,860 Included in Furnace Included in Furnace $ 16,843 $ 16,112 $21,066 $9,538 N/A N/A N/A N/A N/A N/A $ 565,203 Conventional Design Label (Figure 2.3) P-100 E-lOO E-101 PFR-lOO E-102 V-lOO T-102 T-100 r-101 P-lOl K-lOO N/A N/A N/A N/A N/A N/A N/A For Column T-100 For Column T-100 For Column T-100 For Column T-102 For Column T-102 For Column T-102 For Column T-101 For Column T-101 lor Column T-101 Cost $ 20,432 $ 167.332 $ 209,45 1 $51,490 $26,471 $58,219 $35,920 $62,059 $ 22.892 $ 17,108 $83,585 N/A N/A N/A N/A N/A N/A N/A $ 16,112 $21,066 $9,538 $ 9,980 $ 19,452 $9,538 $7,329 $ 12,126 $9,538 S 869,638 31 Table 4.4: Bare module costs ofthe HDA process 1 1 2 3 4 5 6 Equipment ^eed Pump -leat Exchanger "urnace ^eactor(s) Cooler Separator 7 Stabilizer Column 8 9 10 11 12 13 14 15 16 17 18 19 20 21 -n 23 24 25 26 27 Product Column Recycle Column Recycle Pump Recycle Compressor Separator Separator Heat Exchanger Heat Exchanger Heater Heater Cooler Reboiler Condenser Reflux Pump Reboiler Condenser Reflux Pump Reboiler Condenser Reflux Pump Total Modified Design Label (Figure 3.6) P-101 E-lOO Furnace PFR-lOO, PFR-101, PFR-102 E-103 V-lOO N/A T-100 N/A P-lOO N/A V-102 V-lOl E-105 1-.-106 E-101 E-102 E-104 For Column T-100 For Column T-100 For Column T-100 N/A N/A N/A N/A N/A N/A Cost $ 67,628 $286,547 $415,655 $ 220.000 $ 130.915 $ 95,623 N/A $ 133,107 N/A $ 39,454 N/A $ 37,479 $7,107 $45,811 $30,861 Included in Furnace Included in Furnace $55,581 $53,169 $ 65,094 $31,570 N/A N/A N/A N/A N/A N/A $ 1,715,601 Conventional Design Label (Figure 2.3) P-100 E-lOO E-101 PFR-lOO L-102 V-lOO T-102 T-100 T-101 P-101 K-lOO N/A N/A N/A N/A N/A N/A N/A For Column T-100 For Column 1-100 For Column T-100 For Column T-102 For Column T-102 For Column T-102 For Column T-101 For Column T-101 For Column T-101 Cost $ 67,628 $ 1,146,188 $791,724 $912,985 $ 89,563 $419,924 $ 196,385 $216,767 $ 73,208 $ 56,626 $226,619 N/A N/A N/A N/A N/A N/A N/A $53,169 $ 65,094 $31,570 $ 32,934 $ 82,087 $31,570 $24,185 $ 51,172 $31,570 $ 4,600,968 32 Table 4. 5: Total grass roots plant costs oft he HDA process Total Grass Roots Plant Cost Modified Design S 2,733,000 Conventional Design $ 6,337,000 4.3 Performance Comparison . \t this point, it is xxorth highlighting the key benefits and disadvantages oft he moditied HDA design ox er the conventional one. It is also interesting to examine where the main economic benefits oft he modified process arc derived. Table 4.6 provides the main benefits of t he modified design, and Table 4.7 highlights the drawbacks oft he modified design. Table 4.6: Benefits oft he modified design Reactor volume, ft Feed rate to separator svstem, Ibmole/hr Compressor power, hp Stabilizing column Toluene/Diphenyl distillation column Profit, $/hr Grass roots cost ofthe plant, $ Modified Design 2,092.3 974 .5 N/A N/A N/A -74 2 2,733,000 Conventional design 4 ,74 3.5 4 ,4 05.9 1! Needed Needed ,4 4 0 6,337,000 Table 4.7: Disadvantages oft he modified design Total purge rate, Ibmole/hr Total hydrogen purged, Ibmole/hr Modified HDA Process 669.4 6 376.54 Conventional HDA Process 495.38 206.08 From Table 4.6. the modified design provides the following advantages over the conventional process: 1. Profit is 50"0 higher (loss is 50" smaller). 2. Required reactor volume is 56" d smaller. 3. Size of separation sxstem needed is 78"/o smaller. 4. Investment is 43"lower. The only disadx antage ofthe modified process is the higher rate of discharge of unconverted hxdrogen from the plant (376.5 Ibmole/hr \ersus 206.1 Ibmole/hr). From Table 4.7, the modified process discharges about 170 Ibmole/hr of hydrogen more than the conventional process. Hoxxex er, the discharge stream is richer in hydrogen (56.2 mole% versus 41.6 mole%). xvhich makes it a more attractive candidate for hydrogen recoxerx' (see discussion in Chapter 5). Note that exen though the modified HDA process purges more hydrogen than the conventional process, it is more economical because it does not recycle a large gas stream, and the compressor is no longer required. The compressor represents about 10"/o ofthe equipment cost and about 5% ofthe bare module cost. The modified reactor configuration (injecting toluene in the reactor as it is consumed) enables the designer to obtain the same production rate in a smaller reactor volume in comparison to the conventional plug-fiow reactor configuration. In addition, by eliminating the gas recycle stream and the corresponding dilution by methane, the rate of Reaction 1 is higher in the modified HDA process than in the conventional process (see Appendices C and D). Since the toluene is injected at the inlet of each section, the inlet temperatures of sections 2 and 3 can be above 1,150"F, using the energy from Reaction 1 to achiex e higher reaction rate. The modified reactor configuration simplifies the rest ofthe process design in comparison to the conventional design (the recycle column and the recx cle compressor arc not necessary). One additional poim should be examined. Since corrected reaction rate data are used in the design ofthe modified HDA process, it is necessary to examine whether the Table 4.8: Comparison ofthe reactor design based on corrected rate expressions Heat of Reaction 1, BTU/lbmole Heat of Reaction 2, BTU/lbmole Activation Energy of Reaction 1, cal/mole Activation Energy of Reaction 2, cal/iuole Activation Energy of Reaction 3, cal/mole Pre-exponential reaction rate coefficient of Reaction 1. lbmole/min-ft3-psial.5 Pre-exponential reaction rate coefficient of Reaction 2. lbmole/min-ft3-psia2 Pre-exponential reaction rate coefficient of Reaction 3. lbmole/min-ft3-psia2 Toluene flow rate from the reactor, Ibmole/lir Hydrogen flow rate from the reactor, Ibmole/hr Benzene flow rate from the reactor, Ibmole/hr Diphenyl flow rate from the reactor, Ibmole/hr Methane flow rate from the reactor, Ibmole/hr Reactor Volume, ft3 Conventional HDA process xvith the reaction rates used by Luyben et al. [3] -2.150e+04 0 5.09e+04 5.09e+04 5.09e+04 3.69e+06 5.99e+04 2.55e+05 90.64 1,704.26 290.64 4.09 2.282.17 4,743.48 Toluene conversion, % I 75 Conventional HDA process xvith the adjusted reaction rates -2.108e+04 1.05e+04 5.09e+04 3.05e+04 2.47e+04 3.69e+06 0.6272 0.1011 127.81 1,729.61 289.30 1.8 2,257.37 4,743.48 75 3> benefits ofthe modified design are due to the different xalues ofthe rate parameters used and not due to the design itself To examine this, the conventional process was designed xxith the reaction rates used in the literature (for example, in Luyben et al. [3]) and the adjusted reaction rates (see Chapter 2). Table 4.8 presents the design ofthe conventional HDA process obtained using HYSYS.PLANT 2.2 [22] when both sets of rate expressions are used. .Vn examination t)f the xalues in the table rcxeals that the reactor size and the main stream fioxv rates in both cases are almost the saiue. It can be concluded that the difference betxx een the modified and the conx entional designs is due to the difference in the designs and not in the reaction rate parameters. 36 CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS Based on the results obtained in this study, several conclusions can be drawn. Considering the hierarchical structure of ct.nceptual process design, it can be concluded that ^ For chemical processes involving chemical reactions, the design ofthe chemical reactor should be considered as a separate step in the design exercise. This is consistent with the design structure proposed by Smith |6]. -^ The use of a recycle stream should be assessed on the basis of economic considerations rather than an inherent part of the design procedure. These results indicate that the modified hierarchical design structure for chemical processes with chemical reactors proposed by Mann and Hoo [10] deserves further examination. Considering the design ofthe HDA process, it can be concluded that ^ The modified HDA process is much more economical than the conventional HDA process. Specifically, it requires a 70% lower capital investment for construction (bare module cost), and it provides an operating loss 50% smaller than the conventional process. 37 ^ These economic adxantages are obtained mainly due to modifications ofthe reactor configuration, and the elimination ofthe gas recxcle. It is recommended to continue the investigation ofthe modified hierarchical strucmre for the design of chemical processes with chemical reactions. Specifically, it is recommended to: Lxpand the study to consider the dynamic behavior of a process and the design of a plant-wide control structure [29]. This is an essential part of process design, since a design that is solely based on steady- state considerations (as done in this study) docs not assure the operability and controUabilitx ofthe process. It is also recommended to Examine the application ofthe modified hierarchical design structure to other chemical processes with chemical reactions. Such examinations are necessarx to further x'alidate the modified design procedure and to proxide insight into additional potential modifications that may be useful. One possible xariation of both the conventional and moditied HDA processes is adding a unit to separate the methane from the hxdrogen prior to recxcling. Recycling the unconverted hydrogen in the gas recycle stream xvithout removing the methane from it is not desirable due to the fact that methane does not participate in the primary reaction (Reaction 1). This requires larger reactor volume to pass the methane through the reactor. In the conventional HDA design, the methane ce)mposition at the reactor inlet is more than 50"/o (by inolc). As a consequence, this will lead to a larger separation 38 subsystem. Hoxvex'er, recycling the unconverted hydrogen is possible if hydrogen is purified to the same composition as the feed hxdrogen stream (95%). This can be achiexed by applying membrane separation unit to separate the hydrogen from the methane since the high-pressure (about 400 psia) purge stream is available. Note that the high-pressure purge stream in the modified HDA design is richer in hydrogen in comparison to the conventional HDA design. This additional design modification is not considered in this xxork since the objective was to compare the modified HDA process to the conx'entional one. It is recoinmended to extend the analysis ofthe HDA process to designs that include a hydrogen recox cry unit. 39 BIBLIOGRAPHY 1. Douglas, J. M., Conceptual Design ol Cliemical I'roccs.sc.s. New York: McGraxx- Hill(1988). 2. Seider W D., Seader .1. D.. Lcxxin D. R.. Procc.s-.s Design Principles: Synthesis. .Analysis, and Evuliialion. New York: .lohn Wiley & Sons, Inc (1999). 3 Luyben, W. L., Tyreus B. D., Luyben M. L., Plunnvide Process ('onlrol. New York: McGraw-HiU (1998). 4. Mann. U., Principles ofi 'hciuical Reactor Analysis and Design. Lubbock, Texas: Plains Publishing Company (1999). 5. Hougen O. A., Watson K.M. ('hemical Process Prniciplcs: Purl 111. Kinetics and Catalysis. Nexv York: Wilex' (1947). 6. Turton R., Bailie R. C, Whiting W. B.. Shaeiwitz J. A., Analysis. Synthesis, and Design of Chemical Processes. Upper Saddle River, NJ: Prentice Hall, PTR, (1998). 7. Union Carbide Corporation, Basic plwsical properties of pure organic compounds. Laboratory manual. Volume 40-19 (1976). 8. Reklaitis G. V., Introduction to .Material and Energy Balances. New York: John Wiley & Sons, Inc. (1983). 9 Peters M. S., Timmerhaus K. D., Plant Design and Economics for ('hemical Engineers. Fourth Edition. New York: McGraw-Hill. Inc. (1991). 10. Personal communication. Chemical Engineering department, Texas Tech University, Lubbock, Texas. (September 2002). 11. Smith R., Chemical Process Design. New York: McGraw-Hill (1995). 12. McKetta J. J.. Encyclopedia of Chemical I'rocessnig and Design, vol.4. New York: Dekker (1977). 1 3 Silsbv R I Sawyer E. W., "The Dealkylation of Alkyl Aromatic Hydrocarbons I. The Kinetics and Mechanism of Toluene Decomposition m the Presence of Hydrogen," J. Appl. Chem., 6: 347 (August 1956). 40 14. Betts \\'. D., Popper F.. Silsbx R. 1.. -fhe Dealkvlation of Alkyl Aromatic Hydrocarbons If-fhe Dealkylation of Coal l ar Naphthas." J. Appl Chem 7-497 (September 1957). 15. Zinmierman C. C., York R., "Thermal Demethylation of Toluene " l&EC Proc Des. Dev.. 3: 254 (July 1964). 16. Douglas J. M., "A Hierarchical Decision Procedure for Process Synthesis " AlCliE J, 31: 353(1985). 17. Douglas J. M., \\\)odcc)ck D. C.. "Cost Diagrams and the Quick Screening of Process." l&EC Proc. Des. Dev.. 24: 970 (1985). 18. Terill D. L. and Douglas J. M., "1 leat E.xchanger Network Analysis. 1.Optimization." l&EC Research. 26: 685 (1987). 19. Rase H. F., Chemical Reactor Design for Process Plants, vol. 2: ('ase Studies and Design Data New York: Wilex (1977). 20. .Andrecox ich M. J., Westerberg A. W.. "A Single Method on Utilitx Bonding for Heat-Integrated Distillation Sequences" AlChE J.. 31: 363 (1985). 21. Vang V D., Biegler L. T., and Grossmann 1. L.. "Simultaneous Optimization and Heat Integration xvith Process Simulation" Paper no. 72b. 1986 Annual AlChE Meeting, Miami Beach. November 1986 submitted to Computers in Chemical Engineering. 22. Hyprotech Ltd., HYSYS.PLANT 2.2. process simulation software, (2000), Calgary, Canada. 23. National Instruments. HiQ numerical softxxare. (1998). Austin, Texas, USA. 24. Turton R., Bailie R. C. Whiting W B., Shaeiwitz J. A., .-inalysis. .Synthesis, and Design of Chemical Processes. New .lersex': Prentice Hall, PTR, Upper Saddle River (1998). attached software. 25. Levenspiel O., ('hemical Reaction Engineering. New \ork: John Wiley & Sons, Inc. (1999). 26. Biegler L. T.. Grossmann 1. E., Westerberg A. W.. .Systematic .Methods of Chemical Process Design. New .lersex: Prentice Hall, PTR. Upper Saddle River (1999). 27. Chemical Marketing Reporter, December 24. 2000. 41 28. Perry's Chemical Engineer's Handbook, Seventh Edition, McGraw-Hill, NY (1996). 29. \'asbinder li.M.. Hoo K..\.. ".\ Decision-Based Approach to Plantwide Control Structure Synthesis." In press, Ind. Eng. Chem. Res. (2003). 42 APPENDIX A CALCULATION OF THERMODYNAMIC AND KINETIC PARAMETERS 43 This program calculates the thermodynamic and kinetic adjusted parameters for the HDA process. I nput ill format i ou: From Figure 3. 1 (Chapter 3 ot t h i s work), we have t he following val ue: Ea 2 / R v a l u e , d e g r e e K: 1 S 3 6 2 e + 0 4 From Luyben et al . ( 31: E a l / R v a l u e , d e g r e e K: A2, I b mo l e / ( mi n f t 3 p s i a 2 ) A3, I b mo l e / ( mi n f t 3 p s i a Z ) Ea 2 / R v a l u e , d e g r e e K: Ea 3 / R v a l u e , d e g r e e K: 2 5<jl<.>e + 0 4 5 9 8 7 e + 0 4 2 . .55;3e-t 0 5 2 5616e- t 0 4 2 ?. bl 6eH - 04 Push t he green arrow t o c a l c u l a t e t he adj us t ed val ues . Re s ul t s ( adj us t ed val ues ) of t h i s program: He a t of R e a c t i o n 1, B t u / I b mo l e : 2 096e+4 (From Luyben et a l . I 3 ] , t h i s value i s -2.1S0e+04 Etu/lbmole) He a t of R e a c t i o n 2 , B t u / I b mo l e : 1 1 1 8 e + 4 (From Luyben et a l . l 3 ) , t hi s value i s 0 Btu/lbmole) Ea 3 / R v a l u e , d e g r e e K: Al , I b mo l e / ( mi n f t ' 3 p s i a - " 1 . 5 ) A2, I b mo l e / ( mi n f t ^ 3 p s i a ' - Z ) . A3 , I b mo l e / ( mi n f t / - 3 p 3 i a ^ 2 ) : 1 2 2 3 7 e + 0 4 3 6 8 5 8 e + 0 6 0 U21L1 0 0 8 1 2 4 44 d 0 dB dT <m dH 1. 42a - 7; - - 2 . 0 8 e - 6 ; - 2 . 2 9 8 - 6 ; = - 2 . 6 4 a - 7 ; - i . 0 6 e - 7 ; at> " 3 - 9 8 e - l l ; eB - i . OSe - 9 ; eT - l - 1 4 a - 9 ; eM 8 . 0 1 e - l l ; aH - i . 9 2 e - l i The following is the program script for calculating the adjusted kinetic and themiodynamic parameters of reaction rate expressions using HiQ^' [23]. // WotrftioH.- Baasaj M (B) / l>l,stbaiis iM) , Toluszx i' O,- Hy,Jirot,t?n (H).- Dxph&nyl (Z / / Ra a c t i o n 1: T V- H -->- B < M // ^?toic>ix<?ais4ric coefficients f-rjr Rdot j o 1 .ii-: s Tl - 1 ; s Hl - - 1 ; s Bl 1 ; slU - 1; / / R&.actzoiri 2: 2 B > D + H sHZ 1; sBI -2, - sDE = 1,- / / H<ait o f .'^i.-raaSion (Ht) j t 25 d9-i- C i n Jr<5d 1/ t t o2 f r oa "aASJC PHFSrOl i FROFSRTISS OF PURS / / ORSSKIC COMTOUNDS" (J,Jii>ot-,itary J>liliM,i2, Volume -10-19-1976, UtHION CASSIDS) Ht_B 1 9 . 8 2 ; Hf_H = - 1 7 . 8 8 9 ; H_T = 1 1 . 9 S ; H_H 0 ; / / It zs et^,3l to z-Bro 2>y d&fi.siitioi2. Ht_D - 4 3 . SZ; / / Hs^t of Rejctioa 1 (d<^SRl_Z9SJ aMd P.&actl.c.-3 2 (dltaSR2_ZSS) jit 2S asg-retn C in J^oul^/^nale dell:.aH.l_29S (sTl *Hf_T + sHl*H_H + sBl*H_B + sHlH_H) 418S. 8; del t aHI l 2_Z98 " (sH2H_H + sB2''H_B + sD2Hf_D) *418S. 8; ,^/ ld&3il ^^5 ^^At cutD^att3 ,3-, h" -^-. cJ~. &~.:o&tt'lc.rer2ts / / J'ois.T Wzlsy i S.~f2.s, I n c . IS*-.? ipp-Ctl-itS) aH - - 8 3 . 2 ; bC ^ 1. 02S02; cD = - 7 . 2 2 a - 4 ; aB = 1 8 . S ; bB - - 1 . 1 7 e - 2 ; cB 1 . 2 Sa - 3 ; a t 3 1 - S ; bT - 1 . 6 ; e ~ 2 ; cT = 1. 448- 3, aM 3 3 . 4 ; bH - 7 . 3 7 a - i ; cH = 2 . 9 1 e - 4 ; aH 1 7 . 6 ; bH . 7 0 e - 2 ; cH - 1 . 3 1 e - 4 ; / / Hedit cf R&^ctio:.!^ afc s pe oi f i e c ? t eaperd!*ui rs i .?'<?Kl/aiol / / .St r 894. ii K niSO F) de l t a HRl _894 = de l t a HRl _298 t i n t e g r a t e ( c P l , 2 9 3 - I S, 894. i S , t r<i>eoi-') ; / / ^be f'o2 2 oi^-xi^^r v^ltts i s xn Bfe2.t/2h'Jc>2 d e l t a HRl _ Bt u l b a o l e - del t aHAl _894 <9 . 478171i 20313e- 4 j / 2 . i 046226218Se- 3 ; f u n c t i o n c P Kx ) p r o j e c t s T l , s Hl , s Bl , s Hl , a l , aH, aB, aH, bT, bH, bB, bH, cT, cH, oB, cH, dT, dH, dE, dH, eT, eH, eB, sH; y = sTl-' CaT + bT*t: + C T ' K ' Z + dT>-!;'-3 + aT*x-4) + EHl *(aH + bH' x + cH' ::' -2 + dH':t-^3 + eH-x"4) + s Bl ( aB + bB*i! + cB' x' - ^ + dB*x"3 + eB-*x'-4) + s Hl ^i aH + bH*x + cH' x--2 + dH*x' ' 3 + eH' ' x~4) ; r e t u r n y ; e nd a i c t i on; // At T ^ 834.26 K (IISO F) del t aHR2_894 dal t aHR2_298 + i n t e g r a t e I cP2, 2 9 8 . 1 5 , 8 9 4 . 2 6 , <t;r.ii>er.oi.i J ; / / t i j fclloiviav v a i a e zs ia Btu/li>aole del t aHR2_Beul l . mol a del t aHE2_894* ( 9. 478171220313e - 4) / 2. 20462eS218Ea- 3; f u n c t i o n c P2( x) p r o S e c t sHZ, sBZ, 31.2, aH, aB, aD, bH, bB, bD, cH, cE, cf , dH, dB, dK, aH, aB, aD; y - sHZ' -isH + bHx + cHj:-2 < dHx"3 4 eHx^4) + sB2-*CaB + bE^x + cE-'x'-Z + dEx' 3 + KB*X~4) + ED2taI> t bD' x f cD*x'-2 + dl' x~3 + e C x M) ; r e t u m y ; e n d f u n c t i o n ; / / r h. i s p o r t i o n o f thB :,<>ript i,- d^sxp^erf ^ .r*2c!u2,a(- X^^/R .' slu^ Ea2_over _ Val ue_of _Ea2_c. ver _P_degK; del t aHEZ_c' . / Br_R de i t a HR2_Bt ui bt t ol e / ( 1. 987*1. 8) ; Ea3 over _R - BaZ_over _P d6lcaHP2__over_E; / / Thz^ pcr t xo. - . ..t t2-. s c r x p t 1^ d:X9ad t o =. , 2^t . 2. , t a tfc^ A2 ^..d i*^ .....2u / / tar tii^ ^dytzst^d r a t e ^xpi' ^^-sz' -' "^ ,,^., , , , . A2 >a A2 Luyban*ep<- Ea2 ova r _Luyban_de, K/ 894. Z S ) / e ^ i - Sa 2_ova r _E/ 894. 26) ; t l > ' = t 3 : ' u y b a n ^ J S < - Ka 3 : o . . r P _ Lu y b . n _ d a , K/ 8 9 4 . 2 6 ) / e ^ ( - Ha 3 _ o v a r _ P . / 8 9 4 . 2 6 , ; 45 APPENDIX B ECONOMIC DATA 46 VALUES OF CHEMICAL SPECIES Table B.l: Toluene and Benzene price .Material Toluene Benzene Hydrogen S/gal 0.76 0.80 Specific gravity 0.866 0.879 information |27, 28| Water density', lb/gal 8.33 8.33 S/lb 0.105 0.109 Molecular Weight 92 78 (95'%) with 5% methane) S/lbmole 9.66 8.52 1.14 Table B.2: Hydrogen and Methane fuel values information | 1| Material fiydrogen Methane BTU/lbmole* 1.23E+05 3.83E+05 Current Price, $/10''BTU 4.00 4.00 $/lbmole 0.49 1.53 Diphenyl cost information .At this point, there is no published price for treating diphenyl as a waste. In order to be conservative, the price of diphenyl for design is assumed to be $0/lbmole since the conventional HDA process discharges diphenyl (the b\-product considered to be waste) and this discharge may bear some cost, where the modified HDA process does not discharge diphenyl. 47 APPENDIX C THE CONVENTIONAL DESIGN OF HDA PROCESS 48 REFER TO FIGURE 3.3 Table C l ; Conditions and compositions tor all material streams ofthe conventional HDA process Fluid Package: Basis-1 Property Package: UNIQUAC - Ideal Material Stream: H2 Feed CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase I .()()()() 30.00 500.0 49(1.4 9,(134 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0000 0.9700 0.0000 0.0300 0.0000 Material Stream: Recycle Gas CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 45.00 500.0 3519 276.9 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLi; FRACTKJN 0.0009 0.4329 0.0060 0.5602 0.0000 Material Stream: Sep. bottoms CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 45.00 500.0 454.6 272.0 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.2997 0.0038 0.6403 0.0519 0.0044 Material Stream: Sep. inlet CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Overall 0.8978 45.00 500.0 4446 586.0 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0314 0.3891 0.0708 0.5082 0.0004 Material Stream: Toluene Feed CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 26.98 14.70 273.0 190.2 COMPOSITION COMPONENTS Toluene Tlydrogen Benzene Methane BiPhenyl MOLE FRACTION 1.0000 0.0000 0.0000 0.0000 0.0000 49 Table C l continued Material Stream: I CONDITIONS N'apor / Phase FraL'lion Temperature: (C) Pressure, (psia) Molar Flow (Ibmolc'lir) Mass Flow (kii iiiui) Material Stream: 4 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid 1 (I 0(100 30.00 50(1.0 273 0 19(1.2 'base COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane Bd^hcnvl MOLE FRACTION 1OOOO 0.0(100 0 0000 0 0000 0 (1000 Material Stream: 2 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) ()\ erall 0.9673 57.56 .500.0 4LV3 371.9 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0306 0 4838 0.0051 0.4805 0,0000 Mat eri al St ream: 3 CONDI TI ONS Vapor / Phase Fraction Temper at ur e: (C) Pressure: (psia) Mol ar Fl ow (Ibmol e/ hr) Mass Fl ow (kg/ mi n) Liquid Phase 0.0000 137.8 30. 00 123.5 86.03 COMPOSITION COMPONENIS Tol uene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.9995 0.0000 0.0005 0.0000 0. 0000 Mat eri al St ream: 3 (Purge) CONDI TI ONS Vapor / Phase Fraction Temper at ur e: (C) Pressure: (psia) Mol ar Fl ow (Ibmol e/ hr) Mass Fl ow (kg/ mi n) Vapor Phase 1.0000 45. 00 500.0 472. 3 37. 17 C(JMPOSITION COMPONENTS Toluene ll\drogen Benzene Methane BiPhenyl Liquid Phase 0.0000 140.5 500.0 123.5 86.03 Material Stream: 4 (Methane) CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor I 1.0000 -7.401 480.0 23.06 2.635 'base COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLT; FRACTION 0.0009 0.4329 0.0060 0.5602 0.0000 COMPOSITION gg COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.9995 0. 0000 0.0005 0.0000 0. 0000 MOLE FRACTION 0.0000 0.0688 0.0005 0.9307 0.0000 50 Ta b l e d continued Material Stream: 5 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 46.11 505.3 3519 276.9 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0009 0.4329 0.0060 0.5602 0.0000 Material Stream: 5 (Benzene) CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 102.5 30.00 265.5 156.7 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0002 0.0000 0.9997 0.0001 0.0000 Material Stream: 6 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Overall 0.9002 52.62 500.0 4406 562.1 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0907 0.4538 0.0048 0.4507 0.0000 Material Stream: 6 (Diphenyl) CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 196.0 31.00 2.540 2.616 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.2898 0.0000 0.0000 0.0000 0.7102 Material Stream: 7 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.00(10 46.11 505.3 3519 276.9 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0009 0.4330 0.0060 0.5601 0.0000 Material Stream: 8 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 140.5 500.0 123.4 85.98 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.9995 0.0000 0.0005 0.0000 0.0000 51 Table C l continued Material Stream: 9 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 426.7 500.0 4406 562.1 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0907 0.4538 0.0048 0.4507 0.0000 Material Stream: 10 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 62 1.1 500.0 4406 562.1 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTK3N 0.0907 0.4538 0.0048 0.4507 0.0000 Material Stream: 11 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 666.1 500.0 4406 562.1 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0290 0.3926 0.0657 0.5124 0.0004 Material Stream: 12 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Material Stream: 12 1 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Material Stream: 13 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 45.00 500.0 40 02 23.94 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.2997 0.0038 0.6403 0.0519 0.0044 Liquid Phase 0.0000 45.00 500.0 40.02 23.94 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.2994 0.0038 0.6406 0.0519 0.0044 Vapor Phase 1.0000 648.8 500.0 4446 586.0 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRAC TION 0.0314 0.3891 0.0708 0.5082 0.0004 ^^ Table C.I continued Material Stream: 14 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 290.7 500.0 4446 586.0 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0314 0.3891 0.0708 0.5082 0.0004 Material Stream: 15 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Vapor Phase 1.0000 45.00 500.0 3991 314.1 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.0009 0.4329 0.0060 0.5602 0.0000 Material Stream: 16 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 45.00 500.0 414.6 248.0 COMPOSITION CCJMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.2997 0.0038 0.6403 0.0519 0.0044 Material Stream: 17 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 268.1 480.0 391.5 245.4 COMPOSITION C()MPONT: NTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.3173 0.0000 0.6780 O.OOOI 0.0046 Material Stream: 18 CONDITIONS Vapor / Phase Fraction Temperature: (C) Pressure: (psia) Molar Flow (Ibmole/hr) Mass Flow (kg/min) Liquid Phase 0.0000 142.4 33.00 126.0 88.64 COMPOSITION COMPONENTS Toluene Hydrogen Benzene Methane BiPhenyl MOLE FRACTION 0.9852 0.0000 0.0005 0.0000 0.0143 53 Table C.2: Parameters for equipment ofthe conventional HDA process Compressor Compressor: K-lOO Duty: 2.4466e-t-05 cal/min Adiabatic LIT.: 75.00 PolyTropic Eff: 75.00 Furnace Heater: E-101 Duty: 9.846e-^007 caLmin Pressure Drop: 0.0000 psi Cooler Cooler: E-102 Duty: 1.194e-H008 cal/min Pressure Drop: 0.0000 psi V-100 (Separator) Vessel Volume: 276.5 ft3 Level SP: 50.00 % Liquid Volume: 138.2 ft3 Vessel Pressure: 500.0 psia Pressure Drop: 0.0000 psi Duty: 0.0000 cal/min Heat Transfer Mode: Heatinsj Pumps Pump: P-100 Adiabatic Efficiency (%): 75.00 Delta P 485.3 psi Energy: 2.348e+005 calmin Pump: P-101 Adiabatic Efficiency (%): 75.00 Delta P: 470.0 psi Energy: L182e+005 cal/min Heat Exchanger Heat Exchanger: PARAMETERS Exchanger Desig E-lOO n (End Point) Tube Side DeltaP: 0.0000 psi Shell Side DeltaP: 0.0000 psi UA: 1.023e-H005 Btu F-hr Tube Side Data Heat Transfer Coefficient Tube Pressure Drop 0.00 psi Fouling 0.00000 F-hr-ft2/Btu Tube Length Tube O.D. Tube Thickness Tube Pitch Orientation Passes Per Shell Tubes Per Shell Layout Angle TEMA Type 19.69 ft 0.79 in 0.0787 in 1.9685 in Horizontal 6 156 Triangular (30 degrees) Passes: Tolerance: l.OOOOe-04 Shell Side Data Heat Transfer Coefficient Shell Pressure Drop 0.00 psi Fouling 0.00000 F-hr-ft2/Btu Shell Passes Shell Series Shell Parallel Baffle Type Baffle CutC'oArea) Baffle Orientation Spacing Diameter A E L Area 1 10 1 Single 20.00 Horizontal 31 4%l in 28.7430 in 633.03 ft2 54 Table C.2 continued Plug Flow Reactor Plug Flow Reactor: PFR-lOO Physical Parameters Type : User Specified T\ pe Direct Q Value Dimensions Total Volume: 4066 ttj Length: 57.00 ft Diameter: 9.530 ft Number of Tubes: 1 Void Fraction: 1.0000 Pressure Drop: 0.0000 psi Energy Stream : Q Reactor Heat Transfer: Heating Duty : 0.0000 cal/min Wall Thickness: Void Volume: 1.640e-002 ft 4(166 rt3 Initialize From: Reaction Info Reaction Set: Global Rxn Set Integration Information Number of Segments: 20 Minimum Step Fraction: l.Oe-06 Minimum Step Length: 5.7e-05 ft Current R,\n-1 (Kinetic): Stoichiometry, Basis, Parameters STOICHIOMETRY Component Molecular Weight Stoich Coeff Toluene 92.14 -1 Hydrogen 2.016 -1 Benzene 78.11 1 Methane 16.04 1 Balance Error : 0.0000 Reaction Heat: -1.804c BASIS Basis Base Component Rxn Phase Partial Pres Toluene VapourPhase PARAMETERS Forward Reaction Reverse Reaction A : 3.686e-H006 A' : E: 9. 157e- 004 E' : Forward Order 1.000 0.5000 0.0000 0.0000 1004 Btu/lbmole Reverse ()rder (1 0000 0.0000 0.0000 0.0000 Min. Temp (C) -273.1 Max. Temp(C) 3000 Rxn-2 (Kinetic): Stoichiometry, Basis, Parameters STOICHIOMETRY Component Molecular Weight Stoich Coeff Benzene 78.11 -2 BiPhenyl 154.2 1 Hydrogen 2.016 1 Forward Order 2.000 0.0000 0.0000 Balance Error: 0.0000 Reaction Heat: 3490 Btu/lbmole BASIS Basis Base Component Rxn Phase Partial Pres Benzene VapourPhase PARAMETERS Forward Reaction Reverse Reaction A : 0.6272 A' : 0.08124 E : 5.495e-H004 E' : 4.447e+004 Reverse 0.0000 1.000 1.000 Min. Temp (C) -273.1 Order Max. Temp (C) 3000 55 Tabl e C.2 cont i nued Distillation Col umns Distillation: Tra\ Summary Flow Basis: Reflux Ratio: Condenser 1 M;iin TS 2 MLiin IS 3 Main TS 4_Ma i n TS 5 Main IS (1 Mai nTS 7 Mam TS 8 Mai nTS 4 Mai nTS 10 Mai nTS 11 Main IS 12 Mai nTS 13 Main TS 14_Mai n IS 15 Main TS 16 Mai nTS r Mai nTS 18 Mai nTS 19 Mai nTS 20 Mam TS 2 1 Main TS 22 Mam TS 23 Main TS 24_Mai n TS 25 Main TS 26 Main TS 2: ' _Mai n TS ; Reboiler Distillation: T-IOI Tray Summary Tlou Basis: Molar T-100 Molar 3.000 Temp. (C) 102,5 104 0 104 2 104 ^ 104 5 104 7 105.0 105,4 105.9 106.8 108.2 110 2 112.9 116.1 119.3 122 2 126 3 130.4 133,9 136.6 138.4 139.6 140 4 140,9 141.2 I4I.5 141.7 141.9 142 4 Reflux Ratio: 0.5000 Condenser 1 Main TS 2 Main TS 3 Mam TS 4 Main TS 5_Mai n TS 6 Main TS 7 Main I S Reboiler Temp. (C) 137 8 137.8 138.1 138.3 138.6 139.2 139.5 143.0 196,0 Pressure (psia) 30.00 30.00 30.12 30 23 30-35 30 46 30-58 30.69 30,81 30.92 31 04 31.15 31 27 31 38 31.50 31.62 31.73 31.85 31-96 32.08 32 19 32.31 32 42 32.54 32.65 32.77 32.88 33.00 33.00 Pressure (psia) 30.00 30.00 30.17 30.33 30.50 M) 67 30.83 31.00 31.00 Liquid (Ibmole/hr) 796.4 801.8 801.8 801.7 801 5 801.0 800.1 798.4 795,4 79(1 4 782.8 772.7 761.3 751.0 742 9 741.3 737 1 735 2 735 4 736 4 737 6 7-i8.6 739.3 739.9 740.3 740.7 741.0 740.3
Draws (Ibmole/hr) 4.486 V 261.1 L Duties (Btu/hr) -1.248e+007 305.6 40 04 1.413e-i-007 74 Tabl e D.2 cont i nued Heat ers Heater: E-101 Duty: 5 713e+005 Btu/hr Heater: E-102 Duty: 1.260e-i-006 Btu/hr Heater: Fumace Duty: 6.620e-F005 Btu/hr Cool er s Cooler: E-103 Dut\-: 7.700e+006 Btu/hr Cooler: E-104 Dutv 6,394e+0(l4 Btu/hr Pressure Drop (1 1000 psi Pressure Drop: 0.1000 psi Pressure Drop: 0.5000 psi Pressure Drop: 0.5000 psi Pressure Drop: 0.0000 ps Recycle RCV-1 NCMI.RICAL Adj ust s Adjust: ADJ-Tin2 Solving Parameters Adjust: ADJ-Tin3 Solving Parameters Adjust: ADJ-TinI Solving Parameters Pumps Pump: P-100 Adiabatic Efficiency (%): 75.00 Delta P: 485 2 psi Energy: 1.290e+(l()4 Btu/hr Pump: P-101 Adiabatic Efficiency ("o): 75.00 Delta P: 485 3 psi IJiergy: 5.5OOc+004 Btu/hr Pump: P-102 .Adiabatic Efficiency (%) 75.00 Delta P: 3 40(1 psi Energy: 484.6 Btu/hr Recycl es Recycle: RCY-T and D Nl^MFRICAI. Acceleration l>pe: Wegstein Iteration Tvpe Simultaneous Acceleration T>pe: Wegstein Iteration Type: Nested Source Tor Target Value User Supplied Target Value: 1300 F Source for Target Value: User Supplied Target Value: 1300 F Source for Target Value: User Supplied Target Value: 1300 F 75 The following is the reactor Section 1 information in the modified HDA process. 0) 3 -> ra a> Q. E 0) 1320 1300 1280 1260 1240 1220 1200 1180 1160 50 100 150 Reactor length, ft 200 250 Figure D. 1: Temperature profile of Reactor 1 in the modified HDA process SI I e / f t 3 - F 1
R a t e ,
I b
R e a c t i o r
3.OOE-01 2.50E-01 2.00E-01 1.50E-01 1.OOE-01 5.00E-02 O.OOE+00 -5.00E-02 -1.00E-01 Reaction-1 Reactions-2&3 50 100 150 Reactor l ength, ft 200 250 Figure D.2: Reaction rates in Reactor 1 ofthe modified HDA process 76 9.OOE-01 8.OOE-01 7.OOE-01 6.OOE-01 c o g 5.OOE-01 ra u. o> 4 .OOE-01 o 3.OOE-01 - '~~^- ""*--_ 50 100 150 Reactor Lengt h, ft 200 250 -Tol uene - Hydrogen -5r- Benzene ->^-Methane - * - Di phenyl Figure D.3: Component mole fraction in Reactor 1 ofthe modified HDA process 77 The following is the reactor Section 2 information in the modified HDA process. 1320 1300 u. 1280 o ^ 1260 re g. 1240 E - 1220 1200 1180 - - r- ^^ ' h - 1 - - - . J . 1 j ! 1 1 1 100 200 300 400 500 600 Reactor length, ft 700 800 900 Figure D.4: Temperature profile of Reactor 2 in the modified HDA process - h r
CO / f t
o l e
E .o o *. ra CH c o '*> u 0) a: 2.50E-01 2.OOE-01 1.50E-01 1.OOE-01 5.00E-02 O.OOE+00 -5.00E-02 Reaction-1 Reactions-2&3 200 400 600 800 Reactor length, ft 1000 Figure D.5: Reaction rates in Reactor 2 ofthe modified HDA process 78 6.00E-t-02 500E+02 c o o re 0) O 4 .00E-I-02 3.00E+02 2.00E-t-02 1,00E-t-02 O.OOE-^00 c.:.X-X-**-XHXXXX -Toluene -m Hydrogen -& Benzene -^^Methane -^KDiphenyl 0 200 4 00 600 800 1000 Reactor Length, ft Figure D.6: Component mole fracfion in Reactor 2 ofthe modified HDA process 79 The following is the reactor Section 3 information in the modified HDA process. 1310 1300 1290 L l . o 1280 3 1270 0} E 1260 a> 1250 1240 1230 Jf D 100 . . 4 . . . . . . : jAr^ -- . : ---'- i- 200 300 Reactor length. ft - - ' 400 - 500 Figure D.7: Temperature profile of Reactor 3 in the modified HDA process k . s.
V o E a <S * j CC c o +J o ro CC 2.50E-01 2.OOE-01 1.50E-01 1.OOE-01 500E-02 O.OOE+00 Reaction-1 Reactions-2&3 100 200 300 Reactor length, ft ^^S^^^*if4waB^ 400 500 Figure D.8: Reacfion rates in Reactor 3 ofthe modified HDA process 80 c i c t i o
u. 0) M o
5.00E+02 4,50E+02 4.00E+02 3.50E-I-02 3.00E-t-02 2.50E+02 2.00E+02 1.50E+02 1.00E+02 5.00E+01 O.OOE+00 S-H-a-HIHl -B x-)<-^^-x ^ - ^ - -Jk-TftrA*r~AA, 100 200 300 Reactor Length, ft 400 500 -Toluene - Hydrogen -?: Benzene -^<Methane -*-Di phenyl Figure D.9: Component mole fraction in Reactor 3 ofthe modified HDA process 81 Table D,3: Process unit costs for the modified HDA process 1 - 1 4 5 6 7 8 9 10 11 i : 1.3 14 i,> 16 17 18 Equipment Feed Pump Heat Exchanger Furnace Reactors Cooler Separator Product Column Recycle Pump Separator Separator Heat Exchanger Heat Exchanger Heater Heater Cooler Reboiler Condenser Reflux Pump Label* P-101 L-lOO Furnace PFR-lOO, PFR-101, PFR-102 E-103 \ - 100 T-IOO P-100 V-102 V-IOI E-IO.S E-106 E-101 E-102 K-l(14 for Product t olumn T- 100 for Product Column T- 100 for Product C olumn T- 100 Equipment Cost** $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ 20,432 41,833 109,961 195,000 37,584 16,931 31,542 11,920 12,129 2,300 13,152 8,860 Bare Module Cost*** $ $ $ S $ $ s $ $ $ $ s Included in Included in 16,843 16,112 21,066 9,538 $ s $ s 67,628 286,547 415,655 220,000 130,915 95.623 133,107 30,454 37,479 7,107 45.811 30,861 Furnace Furnace 55,581 53,169 65,094 31,570 565,203 $ 1,715,601 * - See Flow Diagram for the modified HDA process (see Chapter 3) ** - Equipment Co.st - equipment cost data adjusted for any ditTerence in unit capacity and elapsed time since the cost material was generated (using cost index). *** - Bare Module Cost - the sum ofthe direct and indirect costs: Direct Cost: a. Equipment f o.b. cost b. Materials required for installation c. Labor to install equipment and material Indirect Cost: a. Freight, insurance, and taxes b. Construction overhead c. Contractor engineering expenses 82 CAPITAL COST ESTIMATION FOR THE MODIFIED HDA PROCESS (using CAPCOSr [24]) Chemical Hngineering Plant Cost Index (CEPCl) Total Purchased Equipment Cost = $ 623,000 Total Bare Module Cost (CS and 0 barg) of Plant Total Bare Module Cost of Plant = $ 1,906,000 Total Module Cost of Plant = $ 2.249,000 Total Grass Roots Cost of Plant = $ 2.733,000 = ^Ri = $ 1.381,000 HEAT EXCHANGERS Heat Exchanger, E-101 Shell and Tube - Fixed Tube Sheet Area (m2) =696.7728 Material of Construction =SS SS Heat E.xchanger, E-102 Kettle Reboiler Area (m2) =50 Material of Construction =CS'CS Tube Side Pressure (barg) =1 FIRED HEATERS Heater. H-l01 Non-Reactive Fired Heater Duty (kWj =984 Tube Pressure (barg) =200 barg PUMPS Pump, P-IOI Centrifugal Pump Material of Construction = Iron Power (kW)= 16.23 Cast Tube Side Pressure (barg) =37 Shell Side Pressure (barg) =37 Equipment Cost = $41,833 Bare Module Cost = $ 286,547 Shell Side Pressure (barg) =1 Equipment Cost = $ 16,112 Bare Module Cost = $ 53,169 Tube Material of Construction=SS Equipment Cost = $ 209,451 Bare Module Cost = $ 791,724 Suction Pressure (barg) = 1 Number of Spares = I Equipment Cost = $ 20.432 Bare Module Cost = $ 67,628 Pump, P-102 Centrifugal Pump Material of Construction Power (kW) = 3,81 Cast Iron Suction Pressure (barg) = 1 Number of Spares = 1 Equipment Cost = $ 1 1,920 Bare Module Cost = $ 39,454 Pump, P-103 Centrifugal Pump Material of Construction = Cast Iron Power (kW) = 0.75 Pump, P-104 Centrifugal Pump Material of Construction = Cast Iron Power (kW) = 2 Suction Pressure (barg) = 1 Number of Spares = 1 Equipment Cost = $ 6,928 Bare Module Cost = $ 22,930 Suction Pressure (barg) = 1 Number of Spares = 1 Equipment Cost = $ 9,538 Bare Module Cost = $31,570 83 TOWERS lower, T-101 Tower Material of Construction= CS Diameter (m) =1.5 Height/Length (m) =10 Pressure (barg) =1,5 Number of Trays =20 Tray Material of Construction= CS Vessel Cost = $31,542 Internals Cost = $ 0 Bare Module Cost = $ 133,107 VESSELS Process Vessel, V-101 Material of Construction = CS Vessel Orientation = Horizontal Diameter (m) = 2.5 Process Vessel, V-102 Material of Construction = CS Vessel Orientation = Horizontal Diameter (m) = 2 Height/Length (in) = 4 Pressure (barg) = 37 Equipment Cost = $ 16,931 Bare Module Cost = $ 95,623 Height/Length (m) = 3 Pressure (barg) = 1 Equipment Cost = $ 12,129 Bare Module Cost = $ 37,479 Process Vessel, V-103 Material of Construction = CS Vessel Orientation = Horizontal Diameter (m) = 0.6 Height/Length (m) = 1 Pressure (barg) = 1 Equipment Cost = $ 2,300 Bare Module Cost = $ 7,107 Process Vessel, V-104 Material of Construction = CS Vessel Orientation = Horizontal Diameter (m) = 2 Height Length (m)= 10 Pressure (barg) = 1 Equipment Cost = $ 21,066 Bare Module Cost = $ 65,094 REACTOR USER ADDED EQUIPMENT User Added Equipment - 10 in Pipe Bare Module Factor (CS -*- 0 barg)= Bare Module Factor (actual)= 1.12 Purchased Equipment Cost = $ 195,000 Bare Module Cost = $ 220,000 Table D.4: Operating cost summary for the moditied HDA process Electrical power: P-100 P-101 P-102 Fuel (Oil or Gas): E-101 E-102 Furnace Cooling water: E-103 ^ E-104 T-UlO Condenser Steam T-100 Rebolier BTU/hr 1.29E-^04 5,50E-H04 4.85E-H02 5.7IE-^05 l,26E+06 6.62E-^05 7.70E+06 6.39E-^04 1.25E-H07 I.4IE+07 Dollars/hr* 0.15 0.64 0,01 2.29 5.04 2.65 0.04 0.04 6.77 242.36 Total 259,98 * based on the utilities prices used by Douglas [1 85 PERMISSION TO COPY In presentmg this thesis m partial fulfillment ofthe requuements for a masters degree at Texas Tech University or Texas Tech University Health Sciences Center, I agree that the Library and my major department shaU make it fi^eely avaUable for research purposes. 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