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

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process control problems. Bisowarno and Tad&"] evaluated the importance of input multiplicity during startup by dynamic simulation. Although several authors simulated the reactive distillation process of ETBE synthesis, output multiplicity was seldom mentioned and the effects of operating parameters on column performance were not discussed thoroughly. 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. Tlvo cases, EG production and synthesis of ETBE, are chosen as the model system using the simulation package ASPEN PLUS, which is widely used for the flowsheet simulation in the process industries"2-'s1. The multiple solutions may be found by performing a sensitivity analysis on one or more parameters, or varying initial guess, the input and output multiplicity thus can be confirmed.

2 BASIC PROCEDURE FOR MULTIPLICITY ANALYSIS In order to analyze the multiplicity in reactive distillation column using ASPEN PLUS, two basic steps are required. Firstly, the reactive distillation column is simulated by the module, RadFrac. For this purpose, ASPEN PLUS requires the specification of components, property method, feed conditions (flow rate, composition and thermal state), operating pressure, column configuration (number of stages, feed location, reaction stage, types of condenser and reboiler), two operating parameters, and reaction type. The two operating parameters can be chosen from a set of parameters such as reflux ratio, distillate rate, bottoms rate, reboiler duty, condenser duty, etc. The reaction type can be chosen from kinetic, equilibrium and conversion. Secondly, sensitivity analysis is carried out to investigate the effects of operating parameters on column performance. As one of model analysis tools, sensitivity analysis provides a feasible method to find multiplicity in reactive distillation column. In the following studies, the option is selected that current results are used as initial estimates for the next step. In this case, only one operating parameter and the initial estimates are variable. Simulations are trivially converged to extreme (very low and very high) values of certain parameter at first, and then the parameter varJune, 2006

ies continuously with a small step towards the other extreme. If divergence occurs, the step size is reduced by half until the step size is small enough. The above simulation procedure is repeated for all possible operating parameters until all interesting cases are converged. After the solution curves are observed and analyzed, the multiplicity existence in the operating region can be determined. It is of interest to discuss why multiple steady states can be found by performing a sensitivity analysis. A typical solution behavior is shown in Fig.1 for the system which is in the region of output multiplicity. When the value of parameter 1 is in the range between a and b, the system has three states, A, B and C with different value of y. In this case, initial guess leads to whether a simulation converges towards the high or low steady state or if divergence occurs. In order to trace steady-state solution paths, the simulations are run outside the region of multiplicity. Once the simulation converges, current results are used as the initial guess, and then a small step is given to parameter 1. According to local convergence of the algorithm, 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. When the solution approaches to the turning point, it will jump from one solution branch to another or divergence will occur. From the behavior of the solution curve, multiplicity and turning points can be determined.

Figure 1 'Qpical behavior of target parameter in the region of output multiplicity

3 RESULTS AND DISCUSSION 3.1 Multiplicity analysis for EG synthesis The hydration of ethylene oxide (EO) is irreversible and proceeds in the presence of a catalyst:

Multiplicity Analysis i n Reactive Distillation Column Using ASPEN PLUS

303

C,H,O

+ H,O --+

C,H,O,

(1)

Simultaneously, a side reaction in which EG reacts with ethylene oxide to yield diethylene glycol (DEG) will take place: (2) Baur et a1.[3'indicated there are two main disadvantages for EG production in a conventional reactor. Firstly, the reaction rate constant of the side reaction is about three times that of the main reaction, therefore a considerable amount of DEG is produced. Secondly, the two reactions are both highly exothermic and require better temperature control. A reactive distillation column offers both the advantages of heat integration and timely removal of the desirable product, EG, to prevent further reaction to DEG Thus, reactive distillation process enhances selectivity, attains better temperature control and avoids hot spot formation. The rate equation and the reaction rate constant were taken from Ciric and Miao'']:
rEG= exp 37.0--

CzH4O + CzH60,

+ C4HloO3

reactions are assumed to occur only in the liquid phase of trays 2-6 because of the presence of a catalyst. The total effective liquid holdup, 2.5m3, is evenly distributed among the reaction trays. All the feed streams enter at boiling point. The WILSON vapor-liquid equilibrium model was used to predict component activities due to the strong non-ideality of the reactive mixture. The operating parameters and their values for the base case are shown in Table 1.
Table 1 The input for the simulation of EG column Feed 1
- . Feed

Feed2 Feed 3 Feed 4 Feed 5 column pressure, Wa distillate to feed ratio boil-up ratio

water 7.31mol.s-' EO 2.24mol.s-' EO 1.39mol-s-' EO 1.32mol-s-' EO 1.34mol.s-' EO 1.36mol.s-' 101.3 0.0 1 15 Stages 2 - 6 10
0.5
~~

( "ya7) ( ";*')

xEox,

(kmd . m-3 . h-I) (3)

Column specification reaction stages total stages

effective liquid holdup per stage, m3

rDEG = exp 37.3 --

xEoxEG (kmol . m-3 . h-' )

(4)
where T is given in K. Figure 2 shows a column configuration used for EG production. This column contains 10 trays including a total condenser and a partial reboiIer. A distillate to feed ratio of 0.01 is maintained. Water feed enters onto the top tray of the column, while the EO feed is distributed along the top section of the column. The
Total condenser Stage 1

To locate the steady states, the effective liquid holdup and boil-up ratio are chosen as the continuation parameters. Fig.3 shows that three steady states are present in a range of holdup volume. The low solution branch can be obtained when the effective liquid holdup is increased from zero. It is of interest to note that there is a sudden increase in EG purity when the effective liquid holdup is increased to 3.9m3. Then, there is an overlap of low branch and intermediate branch when the effective liquid holdup is between

Pressure=l0 I .3kPa

Partial reboiler Products EG, DEG total holdup volume, 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. Ch. E. 14(3) 301 (2006)

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3.9m3and 4.9m3. After the effective liquid holdup is increased to 4.9m3, the divergence occurs. However, if the effective liquid holdup is decreased from 4.9m3, the solution does not trace the same path, and the intermediate branch as shown by the dashed line in Fig.3 is found. When the effective liquid holdup is decreased from very large values, the high solution branch is found. Of course, there are many other methods to find three solution branches. Which solution branch can be found depends on the initial guess fed into ASPEN PLUS. EG mole fraction profiles of the three steady states in the base case are shown in Fig.4 while distribution of other key operation parameters of three steady states in the case of effective liquid holdup reaches 3.8m3 are listed in Table 2.

The solid lines in Fig.4 represent the high solution branch and low solution branch, respectively. The dashed line represents the intermediate solution branch. EG system is a good case to study multiple steady states in reactive distillation process. 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. In the base case, EG purity of low steady state is near to zero and almost no EG is produced. However, in the high steady state EG purity is about 93.5% 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. Fig.5 shows the output multiplicity for a range of boil-up ratio, and the stable solution branches found here are different from
I

.",

0.2 0

\
1 2

4
I I

4 5 6 7 8 stage number from the top

10

10

20

30

40

Flgure 4 EG mole fraction profiles of the three steady states high steady state; 0 intermediate steady state; A low steady state

boil-up ration

Figure 5 Output multiplicity for a wide range of boil-up ratio

(initial guess: 1-4.0001; 2-0.1; 3-0.7; 4-1.0)

Table 2 Distribution of key operation parameters on three steady states via reactive distillation column
Stage number
XEO

Low steady state x w

0.0005

Intermediate steady state

High steady state

XEO
XW

T,K
283.50 284.55 284.58 284.61 284.65 284.68 284.68 284.80 290.90 356.71

XEO

xw

T, K
283.50 284.38 284.40 284.42 284.46 285.63 311.71 362.66 374.65 408.09

T, K
373.06 373.56 373.81 374.07 374.36 375.89 399.79 454.15 469.33 471.91

1 2 3 4
5

0.9995 0.9587 0.9575 0.9562 0.9550 0.9537 0.9537 0.9493 0.7488 0.0844

0.9996 0.9648 0.9642 0.9634 0.9622 0.9185 0.3519 0.0346 0.0026 0.0001

0.0004 0.0306 0.0270 0.0238 0.0214 0.0524 0.6084 0.9227 0.9124 0.3092

0.0003

0.9994 0.9854 0.9763 0.9674 0.9572 0.9059 0.3969

0.0351 0.0305 0.0263 0.0226 0.0194 0.0194 0.0235 0.2158 0.3801

0 0 0 0 0

6 7 8 9 10 Note: xm--EO

0
0 0

0.0420
0.0032 0.0002

mole fraction; x,-water mole fraction.

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previous paper^"^"^'. Here, four distinct stable solution branches based on four different initial guesses of boil-up ratio are compared as example, which are 0.0001, 0.1, 0.7 and 1.0. The simulation results suggest that the initial guess affects strongly the separation capability of a reactive distillation column, and with the increase of the initial boil-up ratio, the separation ability becomes worse. Once the state is determined in one solution branch, it will maintain there stably even at very large or s m d value of boil-up ratio.

4-12 for reaction section, Stages 1-3 for rectifying section and Stages 13-20 for stripping section. Fig.6 shows the column configuration for the base case in detail.
1

Stage 1 Total condenser Feed 1

.
7 d 7

3.2 Multiplicity analysis for ETBE synthesis ETBE has emerged more recently as a potential fuel oxygenate since it can be obtained from renewable bi~-ethanol"~-'~]. In addition, ETBE has superior qualities such as lower blending Reid vapor pressure compared to MTBE. The reactive mixture considered is isobutene (IB) reacting with ethanol (EtOH) to produce the desired product ETBE, in the presence of two inert components (1-butene and cis-Zbutene):
IB + EtOH H ETBE (5) In this reaction, a heterogeneous catalyst, e.g. a strong acidic macro porous ion exchange resin, can be used. An activity-based rate expression has been used to describe the kinetics of ETBE synthesis catalyzed by Amberlyst 15. The reaction rate expression is listed as follows[91:

Feed 2

XI
Stage 19

Stages 4-12

Partial reboiler

Figure 6 ETBE system: Column configuration and specification for simulation by ASPEN PLUS (pressure=700kPa; Feed 1: EtOH-O.312mol~s-'; Feed 2: I B 0.3Omol.s-', l-butene--4.35mol~s-',cis-2-butene-O.35mol~s-'; liquid at boiling point; reflux ratio=5; reboiler duty=76000W, catalyst loading 2kg per stage)

(6) KETBE =10.387+4060.59/T -2.89055hT 0.019151MT +5.28586xm5T25.32977 X 10-*T3 lnK, =-1.0707+1323.1/T (8) (7)

(9) . , exp(40.4 x lo3 RT) where T is given in K. A user kinetic subroutine programmed by FORTRAN was incorporated into the ASPEN PLUS simulation. In this simulation, the vapor-liquid equilibrium is described by the UNIFAC model. The column chosen for ETBE synthesis was basically taken from the paper on dynamic simulation"]. This column has 20 stages, a partial reboiler and a total condenser, Stages

k ,

(mol .kg-' . s-') = 7.418 x 10" x

The composition profiles within the column are shown in Fig.7, where the liquid phase is dominated by 1-butene and cis-2-butene from the condenser down to Stage 16. Below Stage 16, the liquid quickly becomes rich in ETBE because of the temperature increasing. This is reflected in the temperature profile shown in Fig.8. The temperature almost keeps constant from the top stage to Stage 16, but below Stage 16, the temperature increases drastically to 405K when the temperature of reboiler is close to the boiling point of ETBE. These changes are mainly because the large difference between the K-values for ETBE and those for the other four components. The reaction-rate profile shown in Fig.9 indicates that the forward reaction dominates every stage of the reaction section. The largest amount of reaction occurs on Stage 4, where EtOH feed enters, and then it decreases rapidly along the reaction section. However, it increases a little at the end of the reaction section because the IB, 1-butene and cis-2-butene feed enters on Stage 13.
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..

6 8 10 12 14 16 stage number from the top

18

20

Figure 7 Liquid-phase mass fraction profile in the column EtOH; ETBE W IB; 0 1-butene; A cis-2-butene;

boiler duty as shown in Fig.10. Actually, the ETBE reactive distillation is not a special case, for the phenomenon of input multiplicity exists in most reactive distillation columns. Bisowarno and Tadd"] divided the input multiplicity region into separation-controlled and reaction-controlled ones. Below the reboiler duty for the maximum ETBE concentration, the system is controlled by separation process, thus increasing the reboiler duty leads to the improved ETBE purity due to the improved separation. Similarly, increasing the reboiler duty leads to the increase of temperature and ETBE concentration in the reaction zone, and it has a negative effect on the ETBE purity. 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. Fig.11 shows that it exhibits the same phenomena when the reflux ratio is chosen as operating variable with other variables kept constant.

I1
2

I
20

6 8 10 12 14 16 stage number from the top

18

Figure 8 Temperature profile in the column

I
I

0.10

20

40

v)

60 80 100 reboiler duty, kW

120

140

-$ 0.08

E $
Q? w

0.06

Figure 10 Input multiplicities for a variation of reboiler duty in the flxed reflux ratios R=2,7 (other conditions remained the same as those in Fig.6)

0.04
CI

0.02

- - - - - - - - _ _ _ _ _-_ -_ - -_ --____

0
stage number from the top

Figure 9 Reaction rate profile

Input multiplicity as shown in Figs.10 and 11 was found in this ETBE reactive distillation column. In the conventional distillation column, the purity in bottom increases monotonically with the increase of reboiler duty. However, in ETBE reactive distillation process there is a distinct maximum of the desired ETBE product concentration in bottom dependent upon reJune, 2006

! i 0.4! .0.2ti
2 ;

Multiplicity Analysis in Reactive Distillation Column Using ASPEN PLUS

307

It can be known from Fig.12, in the case of R=5, 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. The solid line was obtained as the reboiler duty increased step by step; while the dashed line was obtained as reboiler duty changed in the inverse direction.
I

noted when an optimum design of reactive distillation column is achieved.

REFERENCES
1

Jhon, Y.H., Lee, T.H., Dynamic simulation for reactive distillation with ETBE synthesis, Sep. Pun$ Technol., 31,301-3 17(2003). Tuchlenski, A., Beckmann, A., Reusch. D., Dllssel, R., Weidlich, U., Janowsky, R., Reactive distillation-Industrial applications process design scale-up, Chem. Eng. Sci., 56,387-394(2001). and

2
nn

Baur, R., Higler, A.P., Taylor, R., Krishna, R., Comparison of equilibrium stage and nonequilibrium stage models for reactive distillation, Chem. Eng. J., 76.3337(2000). Chen, F.R., Huss, R.S., Doherty, M.F., Malone, M.F., Multiple steady states in reactive distillation: Kinetic effects, Comput.Chem. Eng., 26, 81-93(2002). Ciric, A.R., Miao, P.Z., Steady state multiplicity in an ethylene glycol reactive distillation column, Ind. Eng. Chem. Res., 33,2738-2748(1994).

4
0.70 60
I

I
85
90

65

70 75 80 reboiler duty, kW

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.6) ------ decreasing reboiler duty; -increasing reboiler duty

Jacobs, R., Krishna, R., Multiple solutions in reactive distillation for methyl tert-butyl ether synthesis, f d . Eng. Chem. Res., 32,1706-1 709( 1993). Baur, R., Taylor, R., Krishina, R., Bifurcation analysis for TAME synthesis in a reactive distillation column: Comparison of pseudo-homogeneous and heterogeneous reaction kinetics models, Chem. Eng. Proc,, 42, 211221(2003). Higler, A.P., Taylor, R., Krishna, R., Nonequilibrium modeling of reactive distillation: Multiple steady states in MTBE synthesis, Chem. Eng. Sci., 54, 13891395(1999).

To our best knowledge, the output multiplicity stated above was seldom reported in ETBE synthesis systems, the desirable operating region is very narrow for the reason that the mass fraction of ETBE in the bottom is extremely high. It means that this process has to be operated with a strict control system. 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. For EG synthesis, output multiplicity was produced with variation of operation parameters such as effective liquid holdup and reflux ratio. A set of stable solution branches which are based on distinct initial guesses are found for a range of boil-up ratio. These results show that a strictly controlled start up is necessary for the EG system. For ETBE synthesis, output multiplicity was found at reflux ratio of 5 over a n m w range of reboiler duty. The input multiplicities were also conf m e d for a variation of reboiler duty at several values of reflux ratio. The multiplicity regions are near to the optimum operation parameters, therefore, it should be

Sneesby, M.G, Tad&, M.O., Datta, R., Smith, T.N., ETBE synthesis via reactive distillation. 1. Steady-state simulation and design aspects, I d . Eng. Chem. Res.. 36, 1855--1869(1997).

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Sneesby, M.G, Tad6, M.O., Datta, R., Smith, T.N., ETBE synthesis via reactive distillation. 2. Dynamic simulation and control aspects, I d . Eng. Chem. Rex, 36, 1870-1881(1997). Bisowarno, B.H., Tad& M.O., Dynamic simulation of startup in ethyl tert-butyl ether reactive distillation with input multiplicity, Ind. Eng. Chem. Res., 39, 19501954(2OOO).

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Venkataraman, S., Chan, W.K., Boston, J.F., Reactive distillation using ASPEN P L U S , Chem. Eng. Prog., 86 (8), 45-54( 1990). Dirk-Faitakis, C.B., Chuang, K.T., Simulation studies of

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catalytic distillation for removal of water from ethanol using a rate-based kinetic model, I d . Eng. Chem. Res., 43,762-768(2004). 17 MOM, K.D., Kienle, A., Gilles, E.D., Rapmund, P., Sundmacher, K., Hoffmann, U., Steady-state multiplicities in reactive distillation columns for the production of fuel ethers MTBE and TAME: Theoretical analysis and experimental verification, Chem. Eng. Sci., 54, 10291043(1999). 18 Yang, S.B., Yang, B.L., Catalytic reactive distillation coupled with pervaporation for synthesizing ethyl tea-butyl ether, J. Chem. Ind. Eng. (China), 52, 950956(2001). (in Chinese) Yang, S.B., Yang, B.L., Wang, H.J., Simulation for the reactive distillation process to synthesize ethyl tert-butyl ether, J. Chem. Eng. Jpn., 34, 1165-1170(2001).

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Hauan, S., Hertzberg, T., Lien, K.M., Multiplicity in reactive distillation of MTBE, Comput. Chem. Eng., 21, 1117-1 124(1997).

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Vadapalli, A., Seader, J.D., A generalized framework for computing bifurcation diagrams using process simulation programs, Comput.Chem. Eng., 25,445-464(2001). Mohl, K.D.,Kienle, A., Gilles, E.D.,Rapmund, P., Sundmacher, K., Hoffmann, U., Nonlinear dynamics of reactive distillation processed for the production of fuel ethers, Comput.Chem. Eng., 21, S989-S994( 1997).

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