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Ind. Eng. Chem. Res.

2011, 50, 14531459

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Selective Hydrogenation of Methylacetylene and Propadiene in an Industrial Process: A Multiobjective Optimization Approach
Wei Wu* and Yu-Lu Li
Department of Chemical and Materials Engineering, National Yunlin UniVersity of Science and Technology, Douliou, Yunlin 64002, Taiwan, R.O.C.

An industrial selective hydrogenation process for methylacetylene (MA) and propadiene (PD) that is mainly composed of two hydrogenation reactors, a separator drum, and a recycle design is presented. According to the specic requirements on the product yield as well as degree of MAPD removal, the optimal operating strategy depends on multiple conicting objectives for the MAPD conversion and the propylene (PP) selectivity. For the multiobjective optimization algorithm subject to prescribed process constraints, the Pareto-optimal solution is obtained via the fuzzy-based membership function and two-phase procedure. Finally, the simulation shows that the desired operating condition regarding ratios of H2 to MAPD at each reactor and the recycle ratio is determined.
1. Introduction For most naphtha-processing plants, propylene (C3-cut) stream usually contains more than 90% propylene (PP) and up to 6% methylacetylene (MA) and propadiene (PD). The MAPD removal mechanism was initially established in the gas-phase process.1,2 To reduce operating cost and increase competitiveness, the liquid-phase operation was often seen in current petrochemical industry.3,4 In general, the kinetic analysis of selective hydrogenation of MAPD was usually addressed via the experimental setup, but the study of the selective hydrogenation of acetylene has been investigated in some kinds of industrial reactors.5,6 Recently, Wang and Froment7 showed the effect of catalyst deactivation for an industrial hydrogenation reactor, and Wu et al.8 introduced kinetic modeling and simulation for the industrial MAPD converter. In the past decades, the basic optimality criterion using the Pontryagin maximum principle has been carried out in xed bed catalytic reactors.9 For exothermic hydrogenation reactions, the traditional dynamic optimization algorithm could regulate the reactor temperature to prevent runways.10 When the production, yield, and selectivity are all considered in the process operation, the suitable operating strategies for an industrial styrene reactor11 would allow performing the multiobjective optimization algorithm. In regard to different objective requirements, the multiobjective optimization technique can be applied to the hybrid power system,12 the polygeneration energy system design,13 and the fed-batch bioreactor.14 To obtain Paretooptimal (a set of equally good) solutions, several multiobjective optimization problems were usually solved by the specic genetic algorithm,15 the advanced evolutionary algorithm,16 and the iterative programming integrated with fuzzy inference.17 On the basis of the same kinetic models, shown in Wu et al.,8 for an industrial MAPD converter, the process operating manner depends on ratios of H2 to MAPD at each reactor and the recycle ratio. To address desired operating manner, the MAPD conversion and the propylene (PP) selectivity are treated as multiple and conicting objectives such that the compromise solutions among the objectives are determined by solving the multiobjective optimization algorithm under prescribed process constraints. To establish a rapid and simple approach for nding
* To whom correspondence should be addressed. E-mail: weiwu@ yuntech.edu.tw.

the Pareto-optimal solution, the iterative programming integrated with fuzzy inference and the two-phase approach are presented. By virtue of computing material and energy balance equations, the feasible operating manner is successfully veried. 2. Process Description Consider the liquid-phase operation of the MAPD-selective hydrogenation process, shown in Figure 1, that is mainly composed of two hydrogenation reactors, a separator drum, and a recycle design. The inlet MAPD stream is mixed with a recycle stream from the vapor-liquid separator drum. The mixed feed ow with an inlet hydrogen stream is fed into the top of the rst reactor (I). For the typically exothermic hydrogenation process, the temperature of outlet stream from the bottom of the rst reactor is higher than the temperature of inlet stream, but the outlet concentration of MAPD is lower than the inlet concentration of MAPD. By exploiting a coolant device and a separator drum, a split outlet stream from the rst reactor ows back as a recycle stream and another stream with a split H2 stream is fed into the top of the second reactor (II). In our approach, the feasible operating manner would to be established step by step under the operating constraints and specications for each industrial reactor. In the rst step, the prescribed kinetic models for each reactor are described as follows. Assumed that the selective hydrogenation reactions including the propylene formation reaction and the formation of oligomers (green oil) are shown by7

Figure 1. Operation analysis of the MAPD converter process.

10.1021/ie100994j 2011 American Chemical Society Published on Web 10/06/2010

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the propylene formation reaction


rPP 9 8 MA + H2 rPD propylene 9 propane 8 PD H2 9 8 rMA

(1)

RPD, RPP, RPN, RC6, RC9]|s)I,II, and Rm represents the recycle ratio for the recycle stream to the inlet stream of the second reactor. (ii) Assuming that each hydrogenation reactor is adiabatic, the overall energy balances for each reactor are written as reactor I: Fr 1 (T - TI) ) r (-Hl) I Vr I,f Fbcpm(Rm + 1) lN l

the oligomer formation reaction 9 C6 + MA 9 C9 8 8


H2 H2 rMA-C
6

(8)
rMA-C
9

2MA + H2 2PD + H2

reactor II:

9 C6 + PD 9 C9 8 8
H2 H2

rPD-C

rPD-C

(2)
9

Fr 1 (T - TII) ) r (-Hl) II Vr II,f Fbcpm lN l

(9)

On the basis of the same kinetic model in Wu et al.,8 all reaction rates for each reactor ( ) I, II) are described by
ri0(crs, Ts) ) ki(Ts)fi(crs, Ts, Kj), s {I, II}, i Nk, j NK

(3)
where crs ) [cH2, cMA, cPD, cPP, cPN, cC6, cC9]|s)I,II, the reaction rate constant ki ) ki0 exp(-Ei/RTs), and the equilibrium constant Kj ) Kj0 exp(Gj/RTs), Nk ) {MA, PD, PP, MA-C6, PD-C6, MAC9, PD-C9, C}, and NK ) {cat-MA, cat-PD, cat-PP, 2, MA, PD, PP, PN, C6, C9}. The nonlinear function for each reaction fi is based on the Langmuir-Hinshelwood/Hougen-Watson (LHHW) kinetic model.1,7,8 If the rate of formation of the deactivating agent is considered, then the original rate equation in eq 3 is modied as ri ) ri0 exp(-RiCc), i Nk

where TI and TII represent the temperature of the rst reactor and the second reactor, respectively. TIf ) (Rm + 1)/(RmTref + TI,f) represents the mixed feed temperature in the rst reactor, and TI,f represents the feed temperature of the rst reactor. Thermodynamic and physical parameters, e.g., the specic heat of bulk uid cpm, bulk density Fb, and heat of reaction of reactant Hl, are assumed to be constant if the variation of each reactor temperature is very small. Remark 1. All kinetic parameters and thermodynamic or physical parameters, e.g., specic heat, density of bulk uid, and reaction heat, have been shown in Wu et al.8 According to the mass and energy balances for each reactor by eqs 6-9, the input-output model of this selective hydrogenation process is established. Moreover, the ratios of H2 to MAPD at each reactor, i.e. H2/MAPD|s)I and H2/MAPD|s)II, and the recycle ratio Rm could affect the product amount of each reactor and indirectly change the temperature of each reactor. 3. Operating Characteristic Analysis For an industrial hydrogenation process operation, the operating temperature for the rst reactor usually ranges from about 320 to 350 K, the operating temperatures for the second reactor ranges from about 300 to 325 K, the pressure ranges from 2.4 to 2.6 bar, and space velocity ranges from 500 to 1000 h-1. According to this industrial specication, the outlet concentration of MAPD of the rst reactor needs to be kept at 3000 ppm (1000 ppm, and the outlet concentration of MAPD of the second reactor should be less than 600 ppm. From those system specications and operating constraints, the desired operating condition with feasible input manipulation will be addressed as follows. Since the inlet concentration of MAPD for both reactors is changed by manipulating H2/MAPD|s)I, H2/MAPD|s)II, and Rm, the systematic analysis of process operating condition depends on normalized operating indexes, including the MAPD conversion (XMAPD), the propylene selectivity (SPP), and temperatures of the rst reactor (NT1) and the second reactor (NT2). XMAPD ) SPP inlet amount of MAPD - outlet amount of MAPD inlet amount of MAPD outlet amount of PP - inlet amount of PP ) inlet amount of MAPD - outlet amount of MAPD outlet temperature at first reactor NT1 operating temperature at first reactor outlet temperature at second reactor NT2 operating temperature at second reactor (10)

(4)

where Cc represents the amount of carbon per unit weight of catalyst and Ri represents deactivation constant for hydrogenation reactions. Moreover, the net rates of formation for each component are shown by RMA ) rMA + 2rMA-C6 + rMA-C9 RPD ) rPD + 2rPD-C6 + rPD-C9 RPP ) rMA + rPD - rPP RPN ) rPP RC6 ) rMA-C6 + rPD-C6 - rMA-C9 - rPD-C9 RC9 ) rMA-C9 + rPD-C9 RH2 ) rMA + rPD + rPP + 2rMA-C6 + 2rPD-C6+ rMA-C9 + rPD-C9 RC ) rC

(5)

In the second step, the operating manner for both reactors and recycle design are introduced into the specic modeling. (i) Assuming that each reactor is well-mixed and recycle time delay is ignored, the mass balances for each composition at each reactor are shown by reactor I: Fr I RrI(crI, TI) I (c - cr ) ) Vr r,f Rm + 1 Fr I (c - crII) ) RrII(crII, TII) Vr r

(6)

reactor II:

(7)

where Fr is the volumetric ow rate in the feed, Vr is volume of each reactor, cr,fI the feed concentration of the rst reactor, and cr,fI ) cr,fI/(Rm + 1) is the mixed feed concentration of the rst reactor. The reaction rate at each reactor is Rrs ) [RH2, RMA,

Remark 2. On the basis of previous mass balances for both reactors, the outlet amounts of MAPD and PP can be evaluated at prescribed values of H2/MAPD at each reactor and recycle ratio. Similarly, the temperature for both reactors can be

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Figure 3. Steady-state operation: (a) SMAPD vs H2/MAPD|s)I and H2/ MAPD|s)II and (b) XMAPD vs H2/MAPD|s)I and H2/MAPD|s)II. Figure 2. Steady-state operation: (a) XMAPD and SPP vs Rm and (b) NT1 and NT2 vs Rm.

evaluated by energy balances for both reactors. By the normalized operating indexes, the operating conditions for prescribed bounds of ratios of H2 to MAPD at each reactor and the recycle ratio from low to high are estimated via the following analyses. When the added H2 amount is xed, the recycle ratio Rm is adjusted from low to high; Figure 2a shows that the increase of recycle ratio can increase the MAPD conversion, but the corresponding PP selectivity gradually decreases. The feed at the rst reactor is diluted by the large recycle ratio such that the reaction rate of the rst reactor becomes slow. Figure 2b shows that the temperature of the rst reactor becomes lower compared to the second reactor while the recycle ratio increases. Since the feed rate at the second reactor decreases due to the increase of recycle ratio, the slow space velocity can improve the conversion of reaction as well as increase the temperature of the second reactor. When the recycle ratio is xed, Figure 3a shows that the PP selectivity depends on different ratios of H2 to MAPD. By the estimated bounds for 1 e H2/MAPD|s)I e 2 and 0 < H2/ MAPD|s)II e 0.5, the high PP selectivity can maximize the yield of propylene. If the upper limits of outlet concentration of MAPD for each reactor are considered, Figure 3b shows that the highest MAPD conversion can be achieved by large ratios of H2 to MAPD at each reactor. Figure 4a,b shows that each temperature distribution of the reactors I and II depends on different ratios of H2 to MAPD. Under the prescribed operating limits, e.g., the outlet concentration of MAPD and operating temperatures for each reactor, the constrained operating points are found by symbolizing the cluster of black or green points depicted in Figures 3 and 4, respectively.

Under the constant recycle ratio and the specied outlet concentration of MAPD and temperatures of each reactor, the feasible operating ranges for the manipulation of both ratios of H2 to MAPD at each reactor can be found by the above gures. According to the estimated bounds 1 e H2/MAPD|s)I, H2/ MAPD|s)II e 3, the corresponding MAPD conversion is close to 0.99 and the PP selectivity is kept at approximately 0.5. 4. Fuzzy-Based Multiobjective Optimization By above analyses of operating indexes vs input effects, the feasible ranges of input manipulations can be found by computing the input-output model, i.e. q(x, u) ) 0

(11)

where the state x ) [crI, crII, TI, TII] and the input u ) [H2/ MAPD|s)I, H2/MAPD|s)II, Rm]. For an industrial MAPD hydrogenation process, the MAPD conversion is expected to be maximized, but the green oil should be minimized, i.e., the highest PP selectivity. It implies that both specic indexes of XMAPD and SPP need to be optimized by virtue of an adequate optimization technique. It has been shown that both XMAPD and SPP are conicting objectives; thus, the multiobjective optimization strategy would turn out to be a trade-off result in which the determination of a compromise set of multiple objectives is usually called the Pareto optimization. To establish a rapid and simple method for solving the multiobjective optimization algorithm, the application of fuzzy set theory is effective. In our approach, the fuzzy membership function in terms of the maximum and minimum values for each objective is shown by

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q(x, u) ) 0 JS - Jmax S JS ) max JS - Jmin S Jmax - Jmin X X 1 e H2 /MAPD| s)I e 3 1 e H2 /MAPD| s)II e 3 Rm g 0 Step 2 (Phase II). Using the product operator for all fuzzy objectives, the results of step 1 are examined by the following formulation max{JS JX}
u

JX )

Jmax - JX X

(14)

(15)

subject to the following constraints q(x, u) ) 0 Ji g Gmax, i {S, X} 1 e H2 /MAPD| s)I e 3 1 e H2 /MAPD| s)II e 3 Rm g 0

(16)

Figure 4. Steady-state operation: (a) NT1 vs H2/MAPD|s)I and H2/MAPD|s)II and (b) NT2 vs H2/MAPD|s)I and H2/MAPD|s)II.

JS )

JX )

where the objectives JS ) SPP and JX ) XMAPD. The upper and lower bounds for each objective are shown by Jmax ) maxuu i Ji and Jmin ) minuu Ji, i {X, S}. u represents the physical i bounds for each input. JS denotes a monotonic increasing membership function, and JX denotes a monotonic decreasing membership function. Moreover, the fuzzy-based multiobjective optimization algorithm is proceeded by utilizing the two-phase procedure.17,18 Step 1 (Phase I). Using the minimum operator for all fuzzy objectives, an optimal solution set is found by maximizing the aggregation function G Gmax ) max min{JS, JX} u ) max G
u

{ {

1, JS g Jmax S JS - Jmax S Jmax S Jmin S Jmin S , Jmin < Ji < Jmax S S

(12a)

0, JS e

1, Jmax - JX X , max JX - Jmin X

JX e JXmin Jmin < JX < Jmax X X Ji g Jmax X

(12b)

0,

Remark 3. Using the fuzzy goals for multiple objectives, the single objective maximization problem in terms of the aggregation function is established in step 1. The two-phase procedures of steps 1 and 2 aim to nd a locally unique solution through the minimum and product operators. Regarding the Pareto optimality in terms of fuzzy objective combinations, it is shown that the Pareto-optimal solution u*, if and only if there does not exist another u u such that Ji(u) g Ji(u*) for all i and Ji(u) g Ji(u*) for at least one i. When two of three input manipulations are xed, the optimal value for one of the inputs is found by using two-phase procedures. The maximal fuzzy objective with respect to one of the input manipulations, H2/MAPD|s)I ) 2.39, is obtained and depicted in Figure 5a. The corresponding two objectives JX and JS are shown in parts b and c of Figure 5, respectively. Obviously, the Pareto-optimal result is veried. In addition, Figure 6 shows that another optimal operating condition is obtained while Rm ) 5. When one of three input manipulations is xed, the optimal solution for two of three inputs is determined by using the twophase procedures. The three-dimenional proles for the aggregation function G with respect to prescribed inputs are shown in Figure 7, in which the optimal solution is pointed with green symbol and the process constraints are covered by black networks. When the input H2/MAPD|s)II is given, the optimal solution for both ratios of H2/MAPD|s)I and Rm can be found by Figure 7a. Similarly, different combinations for two of three inputs are shown in parts b and c of Figure 7, respectively. 5. Conclusions The optimization and simulation of the industrial selective hydrogenation process is addressed. The merits of our approaches are summarized below: (1) With regard to ratios of H2 to MAPD at each reactor and the recycle ratio, the feasible operating manner is established. (2) The MAPD conversion and the propylene selectivity are treated as multiple conicting objectives.

(13)

subject to the following constraints

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Figure 5. Pareto optimality: (a) G vs H2/MAPD|s)I, (b) XMAPD vs H2/ MAPD|s)I, and (c) SPP vs H2/MAPD|s)I.

Figure 6. Pareto optimality: (a) G vs Rm, (b) XMAPD vs Rm, (c) SPP vs Rm.

(3) The multiobjective optimization algorithm subject to prescribed process constraints is solved by virtue of the iterative programming integrated with fuzzy inference. (4) To establish a rapid and simple approach, the calculation using the two-phase procedure is adequate.

In this paper, the Pareto-optimal result can be effectively achieved via the fuzzy-based membership function and the twophase procedure such that the optimal operating conditions are easily veried via the graphic determination.

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Figure 7. Pareto optimality: (a) G vs H2/MAPD|s)I and Rm, (b) G vs H2/MAPD|s)I and H2/MAPD|s)II, and (c) G vs Rm and H2/MAPD|s)II.

Acknowledgment The authors would like to thank the Chinese Petroleum Corp. of the Republic of China and National Science Council

of the Republic of China for nancially supporting this research under Contracts No. EEA9715001 and NSC 982622-E-224-025-CC3.

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Notation
MA ) methylacetylene PD ) propadiene PP ) propylene PN ) propane GO ) green oil crs ) molar concentration of reactant s at prescribed reactor, kmol/m3 s cr,f ) the feed concentration at prescribed reactor, kmol/m3 cpm ) specic heat of bulk uid, kJ/(kg K) Ei ) activation energy of the ith reaction, kJ/kmol Gj ) activation energy of the jth reaction, kJ/kmol Fr ) volumetric ow rate, m3/h ki ) reaction rate constant of the ith reaction ki0 ) preexponential factor of the ith reactant Kj ) equilibrium constant of species j Kj0 ) preexponential factor for equilibrium constant of species j Rm ) recycle ratio Ts ) the temperature at prescribed reactor, K Ts,f ) the feed temperature at prescribed reactor, K Vr ) reactor volume, m3 Greek Symbols Fb ) bulk density, kg/m3 Hl ) heat of the lth reaction, kJ/kmol Rl ) deactivation constant of the lth reaction

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ReceiVed for reView April 30, 2010 ReVised manuscript receiVed August 19, 2010 Accepted September 14, 2010 IE100994J