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Chinese J. Chem. Eng.

, 14(3) 301-308

(2006)

Multiplicity Analysis in Reactive Distillation Column Using ASPEN
PLUS*
YANG Bolun(#2$lf'k)**,WU Jiang(%iI), ZHAO Guosheng(&@ E),WANG Huajun(€qq)
and LU Shiqing( f

m)

State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

Abstract Reactive distillation processes for synthesis of ethylene glycol (EG) and ethyl tert-butyl ether (ETBE)
were modeled with the simulation package ASPEN PLUS. The input multiplicity and output multiplicity were discussed with the method of sensitivity analysis for both cases. In EG production process, steady state multiplicities
were studied in terms of effective liquid holdup volume and boil-up ratio. In ETBE synthesis process, the user kinetic subroutine was supplied into ASPEN PLUS firstly, and then the composition, temperature and reaction-rate
profiles within the reactive distillation column were presented in detail. A set of stable solution branches based on
distinct initial guesses for a range of boil-up ratio were found in EG synthesis. Input multiplicities were observed
for a range of reboiler duty at several values of reflux ratio for ETBE synthesis process. These results can be used to
avoid excessive energy consumption and achieve optimum design of reactive distillation column.
Keywords reactive distillation, ASPEN PLUS, multiplicity, ethyl tea-butyl ether, ethylene glycol

1 INTRODUCTION
Reactive distillation is a multifunction reactor
concept combining chemical reaction and distillati~n"-~'.The integration of reaction and distillation in
one unit may yield several advantages: (1) Selectivity
and conversion can be improved by continuous removal of products from reaction zone; (2) The direct
heat integration decreases the heat demand especially
for strong exothermic reaction, so that hot spot is
therefore avoided; (3) Combination of the reaction and
separation into one unit leads to significant capital
saving; (4) When the feed point is located below the
reaction zone, poisoning of the catalyst can be avoided,
resulting in a longer catalyst life than in the conventional systems.
Due to the interaction between chemical reaction
and distillation, reactive distillation can exhibit intricate nonlinear phenomena and m~ltiplicity[~-~].
Two
types of multiplicities such as input multiplicity and
output multiplicity have been confirmed in reactive
distillation processes.
Input multiplicity refers to the case when the
fmed output states correspond to a multiple set of input variables. It depends on the choice of output or
measured variables, and always associated with the

so-called zero dynamics of the system, which can be
observed by an unexpected inverse response of the
output. On the other hand, output multiplicity indicates the case when the fixed input states correspond
to a multiple set of output states which possibly contain both stable and unstable states. Only stable states
have practical significance, some of the stable states
are desirable, and the rest states are trivial for practical
application.
To design a reactive distillation process, it is important to discover all multiple steady states within the
practical domain of operating variables, to know
whether they are desirable, and to understand how the
column response to changes in operation variables.
For the production of ethylene glycol (EG), Chic
and Miao"' used an equilibrium model with the
homotopy continuation method to show the existence
of multiple steady states. However, only one operation
parameter, the overall effective liquid holdup was investigated, other important operating variables such as
reflux ratio and reboiler duty were not considered in
practical operation.
Sneesby et aZ.[9s'01
described the input multiplicity for the synthesis of ethyl tert-butyl ether (ETBE)
and indicated the significance of input multiplicity for

Received 2005-04-04, accepted 2006-01-31.
Supported by the Key Project of National Natural Science Foundation of China (No.20436040) and the National Natural
Scicnce Foundation of China (No.20176044, No.20476084).
** To whom correspondence should be addressed. E-mail: blunyang@rnail.xjtu.du.cn

*

RadFrac. Although several authors simulated the reactive distillation process of ETBE synthesis. two basic steps are required. the simulations are run outside the region of multiplicity. In order to trace steady-state solution paths. are chosen as the model system using the simulation package ASPEN PLUS. In this case. A typical solution behavior is shown in Fig. it will jump from one solution branch to another or divergence will occur. The multiple solutions may be found by performing a sensitivity analysis on one or more parameters. two operating parameters. etc. condenser duty. the step size is reduced by half until the step size is small enough. According to local convergence of the algorithm. Once the simulation converges. Firstly. only one operating parameter and the initial estimates are variable. sensitivity analysis provides a feasible method to find multiplicity in reactive distillation column. and then a small step is given to parameter 1. operating pressure. B and C with different value of y. the input and output multiplicity thus can be confirmed. column configuration (number of stages. When the solution approaches to the turning point. ASPEN PLUS requires the specification of components. and then the parameter varJune. types of condenser and reboiler). the option is selected that current results are used as initial estimates for the next step. the multiplicity existence in the operating region can be determined. I a h L Figure 1 'Qpical behavior of target parameter in the region of output multiplicity 3 RESULTS AND DISCUSSION 3.3) process control problems.1 Multiplicity analysis for EG synthesis The hydration of ethylene oxide (EO) is irreversible and proceeds in the presence of a catalyst: . If divergence occurs. E. Tlvo cases. When the value of parameter 1 is in the range between a and b. initial guess leads to whether a simulation converges towards the high or low steady state or if divergence occurs. the solution will trace one steady-state solution path and will not deviate it until a turning point such as point c and d is encountered yhen the step is small enough. 14. output multiplicity was seldom mentioned and the effects of operating parameters on column performance were not discussed thoroughly. Secondly. the system has three states. The two operating parameters can be chosen from a set of parameters such as reflux ratio. No. which is widely used for the flowsheet simulation in the process industries"2-'s1. (Vol. the reactive distillation column is simulated by the module. Ch. 2006 ies continuously with a small step towards the other extreme. reaction stage. For this purpose. equilibrium and conversion. Simulations are trivially converged to extreme (very low and very high) values of certain parameter at first. Bisowarno and Tad&"] evaluated the importance of input multiplicity during startup by dynamic simulation. reboiler duty. In the following studies. property method. After the solution curves are observed and analyzed. and reaction type.302 Chinese J. 2 BASIC PROCEDURE FOR MULTIPLICITY ANALYSIS In order to analyze the multiplicity in reactive distillation column using ASPEN PLUS. sensitivity analysis is carried out to investigate the effects of operating parameters on column performance. As one of model analysis tools. feed location. The reaction type can be chosen from kinetic. A. multiplicity and turning points can be determined. It is of interest to discuss why multiple steady states can be found by performing a sensitivity analysis. EG production and synthesis of ETBE. current results are used as the initial guess. distillate rate. The above simulation procedure is repeated for all possible operating parameters until all interesting cases are converged. or varying initial guess. The objective of this paper is to analyze and discuss steady-state multiplicity more thoroughly and comprehensively by considering more operation parameters in reactive distillation column.1 for the system which is in the region of output multiplicity. From the behavior of the solution curve. In this case. feed conditions (flow rate. bottoms rate. composition and thermal state).

to prevent further reaction to DEG Thus. reactive distillation process enhances selectivity. m3 0.34mol.O --+ C.31mol. +C4HloO3 (2) Baur et a1.O + H. Secondly.H. h-I) (3) reactions are assumed to occur only in the liquid phase of trays 2-6 because of the presence of a catalyst.303 Multiplicity Analysis in Reactive Distillation Column Using ASPEN PLUS C.. Water feed enters onto the top tray of the column.9m3.s-' EO 1. The operating parameters and their values for the base case are shown in Table 1.0-- ( ". Firstly.5 ~~ xEoxEG (kmol .01 is maintained. Then. 2. while the EO feed is distributed along the top section of the column. the two reactions are both highly exothermic and require better temperature control.O. The WILSON vapor-liquid equilibrium model was used to predict component activities due to the strong non-ideality of the reactive mixture. All the feed streams enter at boiling point. (kmd .s-' EO 2. attains better temperature control and avoids hot spot formation. DEG total holdup volume.[3'indicated there are two main disadvantages for EG production in a conventional reactor. Fig. E. the reaction rate constant of the side reaction is about three times that of the main reaction. there is an overlap of low branch and intermediate branch when the effective liquid holdup is between Total condenser Stage 1 Pressure=l0 I .36mol.5m3. A distillate to feed ratio of 0.39mol-s-' EO 1. The total effective liquid holdup. (1) Simultaneously. The rate equation and the reaction rate constant were taken from Ciric and Miao'']: ( "ya7) rEG= exp 37.s-' EO 1.24mol.3kPa Partial reboiler Products EG. The low solution branch can be obtained when the effective liquid holdup is increased from zero. the effective liquid holdup and boil-up ratio are chosen as the continuation parameters. m-3 . therefore a considerable amount of DEG is produced.6 10 distillate to feed ratio boil-up ratio Column specification reaction stages total stages effective liquid holdup per stage. A reactive distillation column offers both the advantages of heat integration and timely removal of the desirable product.32mol-s-' EO 1.3 0. The To locate the steady states. m3 Figure 2 EG system: Column configuration and specification for simulation by ASPEN PLUS Figure 3 Output multiplidties for a variation of effective liquid holdup Chinese J. h-' ) (4) where T is given in K. 14(3) 301 (2006) .3 shows that three steady states are present in a range of holdup volume. Figure 2 shows a column configuration used for EG production.H. is evenly distributed among the reaction trays. m-3 .3 -- xEox.*') rDEG= exp 37.0 1 15 Stages 2 . Table 1 The input for the simulation of EG column Feed 1 . EG. Wa 101. It is of interest to note that there is a sudden increase in EG purity when the effective liquid holdup is increased to 3. This column contains 10 trays including a total condenser and a partial reboiIer. Feed water 7. a side reaction in which EG reacts with ethylene oxide to yield diethylene glycol (DEG)will take place: CzH4O + CzH60. Ch.s-' Feed2 Feed 3 Feed 4 Feed 5 column pressure.

9493 0.5% and a large amount of EO react with water to produce EG Output multiplicities are also found when other operating variables such as boil-up ratio are chosen as continuation parameters. EG system is a good case to study multiple steady states in reactive distillation process. the high solution branch is found.9537 0.33 0.0194 284.9634 0. there are many other methods to find three solution branches.0420 454. The solid lines in Fig.0001 0.89 7 0. 4-1.3 is found. in the high steady state EG purity is about 93. Of course.55 0.".50 0.06 2 0. x.6084 311. EG mole fraction profiles of the three steady states in the base case are shown in Fig.K XEO xw T.56 0 0.9995 0. the solution does not trace the same path.304 Chinese J.40 4 0. 0 intermediate steady state. E.9854 373. EG purity of low steady state is near to zero and almost no EG is produced.07 5 0. and the stable solution branches found here are different from I .68 0.71 0.9622 0. 3-0. 2-0.79 8 0.2158 290. if the effective liquid holdup is decreased from 4.63 0 0. In this system three multiple states exist in a wide range and the difference between low steady state and high steady state is very interesting.1.9227 362.3092 408.58 0. 14.7. However. Fig.0) Table 2 Distribution of key operation parameters on three steady states via reactive distillation column Low steady state Stage number Intermediate steady state High steady state XEO xw T.38 0 0.65 0.9124 374. When the effective liquid holdup is decreased from very large values.9674 374.9648 0.0004 283.0263 284.-water mole fraction.0214 284.91 10 Note: xm--EO June. 2006 mole fraction.0270 284.3) 3.36 6 0. (Vol.0524 285.66 0 0.3519 0.4 represent the high solution branch and low solution branch.81 3 0. .7488 0.9642 0.9m3and 4.80 0.0026 0.0351 284.3969 399. Which solution branch can be found depends on the initial guess fed into ASPEN PLUS. Ch.9537 0.9996 0.9562 0.0226 284.61 0. A low steady state Figure 5 Output multiplicity for a wide range of boil-up ratio (initial guess: 1-4.0003 0.0306 284.0305 284. However. the divergence occurs.71 0 0.9994 373.90 0.0032 469.4 while distribution of other key operation parameters of three steady states in the case of effective liquid holdup reaches 3.9m3.9059 375.9575 0.65 0 0.09 0 0.9550 0.9185 0. K XEO XW T.9m3. In the base case.0235 284. The dashed line represents the intermediate solution branch. respectively.0844 0. No. K 1 0. 4 10 I 0 10 I I 20 30 40 boil-up ration Flgure 4 EG mole fraction profiles of the three steady states high steady state.0194 284.8m3 are listed in Table 2.9587 0.0005 283.0002 471.9572 374.0238 284.0346 0.50 0. I 0.5 shows the output multiplicity for a range of boil-up ratio. After the effective liquid holdup is increased to 4.9763 373.15 9 0.68 0. and the intermediate branch as shown by the dashed line in Fig.2 - \ 0 1 2 3 4 5 6 7 8 stage number from the top 9 .3801 356.9m3.46 0 0.42 0 0.0001.

a heterogeneous catalyst. catalyst loading 2kg per stage) The composition profiles within the column are shown in Fig. E. Feed 1: EtOH-O.6 shows the column configuration for the base case in detail.59/T -2.418 x 10" x (8) (9) . Chioese J. The simulation results suggest that the initial guess affects strongly the separation capability of a reactive distillation column.3Omol. 0. liquid at boiling point. four distinct stable solution branches based on four different initial guesses of boil-up ratio are compared as example. but below Stage 16. where EtOH feed enters.1. the vapor-liquid equilibrium is described by the UNIFAC model.s-'. An activity-based rate expression has been used to describe the kinetics of ETBE synthesis catalyzed by Amberlyst 15.32977 X 10-*T3 lnK. The largest amount of reaction occurs on Stage 4. exp(40. =-1.cis-2-butene-O. reboiler duty=76000W. (mol . . 4-12 for reaction section. In addition. the liquid quickly becomes rich in ETBE because of the temperature increasing.387+4060. This column has 20 stages.35mol~s-'.305 Multiplicity Analysis in Reactive Distillation Column Using ASPEN PLUS previous paper^"^"^'. 14(3) 301 (Zooa) . 0.0. s-') = 7.1/T k.4 x lo3 RT) where T is given in K. Here.9 indicates that the forward reaction dominates every stage of the reaction section.2 Multiplicity analysis for ETBE synthesis ETBE has emerged more recently as a potential fuel oxygenate since it can be obtained from renewable bi~-ethanol"~-'~].0001.019151MT +5. and with the increase of the initial boil-up ratio.kg-' .312mol~s-'. These changes are mainly because the large difference between the K-values for ETBE and those for the other four components. Fig. This is reflected in the temperature profile shown in Fig. The reactive mixture considered is isobutene (IB) reacting with ethanol (EtOH) to produce the desired product ETBE. Stages 1-3 for rectifying section and Stages 13-20 for stripping section.8.28586xm5T2- (7) 5. l-butene--4. Feed 2: IB0. and then it decreases rapidly along the reaction section.35mol~s-'. which are 0. 7 3. 1 Stage 1 Total condenser Feed 1 . where the liquid phase is dominated by 1-butene and cis-2-butene from the condenser down to Stage 16. However. can be used. the temperature increases drastically to 405K when the temperature of reboiler is close to the boiling point of ETBE. 1-butene and cis-2-butene feed enters on Stage 13. reflux ratio=5. The column chosen for ETBE synthesis was basically taken from the paper on dynamic simulation"]. it will maintain there stably even at very large or s m d value of boil-up ratio. The reaction-rate profile shown in Fig. it increases a little at the end of the reaction section because the IB. a partial reboiler and a total condenser. Ch. A user kinetic subroutine programmed by FORTRAN was incorporated into the ASPEN PLUS simulation. The temperature almost keeps constant from the top stage to Stage 16. the separation ability becomes worse.89055hT 0. Stages Feed 2 d 7 XI Stages 4-12 Stage 19 Partial reboiler Figure 6 ETBE system: Column configuration and specification for simulation by ASPEN PLUS (pressure=700kPa. e.7. In this simulation. ETBE has superior qualities such as lower blending Reid vapor pressure compared to MTBE. a strong acidic macro porous ion exchange resin.0707+1323.7 and 1. The reaction rate expression is listed as follows[91: (6) KETBE=10. in the presence of two inert components (1-butene and cis-Zbutene): IB + EtOH HETBE (5) In this reaction. Once the state is determined in one solution branch. Below Stage 16.g.

14.2.10 and 11 was found in this ETBE reactive distillation column.6) v) -$ 0.. 2006 !i 0. the system is controlled by separation process. Similarly..04 CI 2 . .. E. Actually. . kW I 120 140 Figure 10 Input multiplicities for a variation of reboiler duty in the flxed reflux ratios R=2.. + I1 I 2 4 I I I I I 1 6 8 10 12 14 16 stage number from the top I I 18 20 boiler duty as shown in Fig. thus increasing the reboiler duty leads to the improved ETBE purity due to the improved separation. the ETBE reactive distillation is not a special case. A cis-2-butene.10. Fig. for the phenomenon of input multiplicity exists in most reactive distillation columns. In the conventional distillation column. the purity in bottom increases monotonically with the increase of reboiler duty.10 - I I 60 80 100 reboiler duty.-_.11 shows that it exhibits the same phenomena when the reflux ratio is chosen as operating variable with other variables kept constant.ti 2 . 0 1-butene. Ch._. and it has a negative effect on the ETBE purity._ _ _ _ _-_. in ETBE reactive distillation process there is a distinct maximum of the desired ETBE product concentration in bottom dependent upon reJune. However.7 (other conditions remained the same as those in Fig.08 E $ 40 0..06 Q? w 0.02 0 stage number from the top Figure 9 Reaction rate profile Input multiplicity as shown in Figs.. 2 6 8 10 12 14 16 stage number from the top 4 18 20 Figure 7 Liquid-phase mass fraction profile in the column EtOH. Bisowarno and Tadd"] divided the input multiplicity region into separation-controlled and reaction-controlled ones.4!0. It is reflected in the reaction-controlled region on the right-hand side of the maximum that the ETBE purity decreases with the increasing reboiler duty. (Vol. No3) 306 . Below the reboiler duty for the maximum ETBE concentration.._ _ _ _ 0.Chinese J.. Figure 8 Temperature profile in the column I 20 0. ETBE W IB.. increasing the reboiler duty leads to the increase of temperature and ETBE concentration in the reaction zone.

. Higler.. Dirk-Faitakis.2738-2748(1994). I d .. Eng. output multiplicity was produced with variation of operation parameters such as effective liquid holdup and reflux ratio. Res. 13891395(1999). Weidlich.. Higler. “ETBE synthesis via reactive distillation. Proc. M..G. Sci.. Chem.. Reusch. it should be 307 5 and Baur. the output multiplicity stated above was seldom reported in ETBE synthesis systems. R. R.N. A. Chan. M.. “Reactive distillation using ASPEN P L U S . K. Krishna. U..O. 1870-1881(1997).6) -----. R. Eng.. R... A set of stable solution branches which are based on distinct initial guesses are found for a range of boil-up ratio. R. Datta. Res. 32.. A.H.. Chem. Tad6. “ETBE synthesis via reactive distillation. A. Sci. 7 Baur.. Chem. M. 1. Datta. “Nonequilibrium 8 modeling of reactive distillation: Multiple steady states in MTBE synthesis”. 39. A. “Multiple steady states in reactive distillation: Kinetic effects”. 3 4 0.Eng.F. 6 Jacobs. Eng. Taylor. 42. Taylor.H..P. Eng.B.. Smith.3337(2000). Krishna.. Chem..387-394(2001). therefore. Dynamic simulation and control aspects”. REFERENCES 1 Jhon. M.. Ciric.P. For EG synthesis.F. Chem. Id. Lee.R. Huss. The multiplicity regions are near to the optimum operation parameters.. Janowsky. R.. 26. T. Chem. P. Doherty. R.O. R. “Dynamic simulation of startup in ethyl tert-butyl ether reactive distillation with input multiplicity”. A. Ind. “Reactive distillation-Industrial applications process design scale-up”. 2 I nn Tuchlenski. Krishna. J. B.O.H. 9 Sneesby. Res. Dllssel. 14(3) 301 (2006) . R. M. R... Smith. 86 (8). 54.T.70 60 I 65 I I 4 70 75 80 reboiler duty.decreasing reboiler duty. These results show that a strictly controlled start up is necessary for the EG system.S... the output multiplicity exists near the optimum reboiler duty although the region is very narrow and the gap between high state and low state is small. R. 81-93(2002).Multiplicity Analysis in Reactive Distillation Column Using ASPEN PLUS It can be known from Fig.F. “Steady state multiplicity in an ethylene glycol reactive distillation column”. Miao. Eng. fd. 45-54( 1990).. -increasing reboiler duty To our best knowledge. 12 13 Venkataraman. Comput. kW 85 90 Figure 12 Output multiplicity for a variation of reboiler duty and fured reflux ratio R=5 (other conditions remained the same as those in Fig. noted when an optimum design of reactive distillation column is achieved.. T.. 10 11 Sneesby.. Krishina. S. R. Chem. Steady-state simulation and design aspects“.. Chuang. Chem..K.. “Comparison of equilibrium stage and nonequilibrium stage models for reactive distillation”. Res.Z.N.. Eng. Tad&. Sep.. For ETBE synthesis. the desirable operating region is very narrow for the reason that the mass fraction of ETBE in the bottom is extremely high. 19501954(2OOO). in the case of R=5. The input multiplicities were also conf m e d for a variation of reboiler duty at several values of reflux ratio. Eng.G. 4 CONCLUSIONS Multiple steady states were found in reactive distillation for both EG production and ETBE synthesis processes by the method of sensitivity analysis with different initial guess of the solution. “Dynamic simulation for reactive distillation with ETBE synthesis”. C. Eng. Malone. J.. F. The solid line was obtained as the reboiler duty increased step by step. Taylor... Pun$ Technol....12. 211221(2003). 33. “Simulation studies of Chinese J.... Ch. output multiplicity was found at reflux ratio of 5 over a n m w range of reboiler duty. Y. Rex. 36. Chem. Boston. M.. “Multiple solutions in reactive distillation for methyl tert-butyl ether synthesis”. E.301-3 17(2003). 56. R. W. T. It means that this process has to be operated with a strict control system. R... D. Chem. 31. “Bifurcation analysis for TAME synthesis in a reactive distillation column: Comparison of pseudo-homogeneous and heterogeneous reaction kinetics models”.. Tad& M.1706-1 709( 1993).. 2. Eng.. Eng. Bisowarno.R.Chem. 1855--1869(1997). Chen. 36. 76. R. Beckmann. Ind. while the dashed line was obtained as reboiler duty changed in the inverse direction. Prog.

T. Mohl. Comput.. A. 950956(2001). 21. Kienle. 21. Wang.D. (Vol. Sundmacher..Chem. J. Chem.Chem.. Gilles. Chem. (in Chinese) Yang. 14.M..L. S. reactive distillation of MTBE”.D. Seader. “Catalytic reactive distillation coupled with pervaporation for synthesizing ethyl tea-butyl ether”.D... Chem. K.. Sci. E. S989-S994( 1997).. E.. Eng. 1117-1 124(1997). . “Nonlinear dynamics of reactive distillation processed for the production of fuel ethers”.D. Comput. 54. Eng. Rapmund. Hoffmann. B.L. S. No3) 308 catalytic distillation for removal of water from ethanol using a rate-based kinetic model”.Rapmund. 2006 MOM.. Chem. K. 43. Eng.D. 14 17 Hauan.B. U..... H. Eng.. J. Yang.. P. U. “Multiplicity in fuel ethers MTBE and TAME: Theoretical analysis and experimental verification”. Ind. Gilles. E.. 10291043(1999). 1165-1170(2001). A. K..B. Res.. 52. 25.445-464(2001).762-768(2004)...Chinese J. “A generalized framework for computing bifurcation diagrams using process simulation 18 programs”.Eng..J. Hoffmann.. Lien..Kienle. June. 34. Id. “Steady-state multiplicities in reactive distillation columns for the production of 19 Yang.. K. Eng.. (China).. J. B. A. Chem. S. 15 16 Vadapalli. Ch. Hertzberg. Yang. K. Jpn. “Simulation for the reactive distillation process to synthesize ethyl tert-butyl ether”. Comput. P. Eng.. Sundmacher.