Chinese Journal of Chemical Engineering, 16(1) 100103 (2008)

Hybrid Process of Reactive Distillation and Pervaporation for the Production of Tert-amyl Ethyl Ether
Amornchai Arpornwichanop1,*, Ukrit Sahapatsombud2, Yaneeporn Patcharavorachot1 and Suttichai Assabumrungrat2

1 Control and Systems Engineering Research Center, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand 2 Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand

Abstract In this study, a reactive distillation column in which chemical reaction and separation occur simultaneously is applied for the synthesis of tert-amyl ethyl ether (TAEE) from ethanol (EtOH) and tert-amyl alcohol (TAA). Pervaporation, an efficient membrane separation technique, is integrated with the reactive distillation for enhancing the efficiency of TAEE production. A user-defined Fortran subroutine of a pervaporation unit is developed, allowing the design and simulation of the hybrid process of reactive distillation and pervaporation in Aspen Plus simulator. The performance of such a hybrid process is analyzed and the results indicate that the integration of the reactive distillation with the pervaporation increases the conversion of TAA and the purity of TAEE product, compared with the conventional reactive distillation. Keywords reactive distillation, pervaporation, hybrid process, tert-amyl ethyl ether

INTRODUCTION

Tertiary ethers as oxygenated compounds have become important additives for enhancing the combustion efficiency of gasoline. Amongst the tertiary ethers, methyl tert-buthyl ether (MTBE) has been widely used in many countries and is currently produced in large-scale production. However, it has been reported that MTBE may pollute underground water due to its high water solubility [1]. Therefore, the production of other oxygenated compounds, such as tertiary-amyl methyl ether (TAME) and tertiary-amyl ethyl ether (TAEE) have been of present interest. Compared with TAME, TAEE is a more favorable choice in the environmental point of view as ethanol, one of the reactants, can be derived renewably from agricultural products, such as sugar cane, corn and potatoes. Most of the previous studies considered the production of TAEE from isoamylene (IA) and ethanol (EtOH) in reactive distillation [2, 3]. Tertiary amyl alcohol (TAA), a main component in fusel oil which is a byproduct from fermentation processes for ethanol production, can be an alternative reactant instead of IA. Therefore, the synthesis of TAEE from TAA and EtOH should be a promising route as both reactants are derived from renewable resources [4]. The previous study [5] investigated the application of a reactive distillation (RD) for TAEE production from TAA and EtOH. It has been shown that the RD is a favorable alternative process since the conversion beyond an equilibrium limitation can be achieved. However, the integration of the RD with other unit operations for water removal should be considered to improve its performance. In this study, a hybrid reactive distillationpervaporation process is applied for the synthesis of TAEE from EtOH and TAA. A rate-based kinetic model for liquid-phase etherification and an equilibrium stage model for separation are used to study the

reactive distillation. A model of a pervaporation unit is developed and implemented in Aspen Plus. The simulations are performed to examine the effects of operating parameters; the flow rate and the location of a side stream to the pervaporation unit, on the performance of reactive distillation. 2 MODEL OF A HYBRID REACTIVE DISTILLATION-PERVAPORATION PROCESS 2.1 Reactive distillation model

The RADFRAC model, a rigorous equilibriumstage distillation model in Aspen Plus, is used to represent a reactive distillation (RD) column. The configuration of the RD column for TAEE production used here is based on the previous study [5]. It consists of 14 stages numbered from the top. This includes a total condenser being the first stage and a partial reboiler being the last stage. The RD column is divided into two sections: the reaction section represented by 4 reactive stages (2-5) and the stripping section represented by 8 stages (6-13). The combined feed of TAA and EtOH is introduced at the top of the reaction section (Stage 2). 2.2 Pervaporation model

A model of a pervaporation (PV) unit is developed in Fortran subroutine and implemented in Aspen Plus to investigate the performance of a hybrid process of RD and PV. It is assumed that there is no reaction occurring in the PV. Fig. 1 shows the schematic diagram of the PV membrane unit. By performing a mass balance around the PV unit at steady state conditions; the following equation is obtained. (1) Ff ,i = Fr,i + APi xi

Received 2007-05-18, accepted 2007-10-27. * To whom correspondence should be addressed. E-mail: Amornchai.A@chula.ac.th

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Figure 1

Schematic diagram of a PV unit

where, Fi and Pi are the molar flow rate (mols 1) and the permeation rate (mols 1m 2) of component i. Equations (2) to (5) show the permeation rate of each component through the zeolite membrane [6]. It is noted that the permeation of TAEE is negligibly small. 1046 PTAA = exp 5.4 (2) T PEtOH 1247 = exp 5.4 T (3) (4)

Figure 2

A hybrid reactive distillation-pervaporation process

2656 PIA = exp 2.1 T

3656 PH 2O = exp 9.4 (5) T The temperature of retentate and permeate streams is calculated by solving an energy balance around the PV unit which is assumed to be operated under adiabatic condition. The energy balance can be expressed as follows, H f ,i = H r,i + H p,i (6) where, Hi is the enthalpy of component i in each stream. Figure 2 demonstrates a hybrid reactive distillationpervaporation process. The column specification and feed conditions of such a process are given in Table 1. It is noted that the two additional input parameters of the column configuration specified for the simulation of the RADFRAC model are reboiler heat duty (Qr) and reflux ratio (R). 2.3 Kinetic model

of TAA with EtOH in the liquid phase over Amberlyst 15 as a commercial acid catalyst and is inhibited by two undesired side reactions: the dehydration of TAA to IA and the etherification of the IA produced to TAEE. Although IA can be represented by two isomers: 2-methyl-1-butene (2M1B) and 2-methyl-2butene (2M2B), they are lumped together with the properties of the major isomer 2M2B. The reaction scheme for the liquid phase synthesis of TAEE from TAA and EtOH taking place in the reaction section of RD is shown in Eqs. (7) to (9).

TAA + EtOH
TAA IA + EtOH

TAEE + H 2 O
IA + H 2 O TAEE

(7)
(8) (9)

The kinetic rate equations of the above reactions can be expressed in terms of mole fractions as follows [5], xTAEE xH 2O rEtOH = mr Q k1 xEtOH xTAA + K Eq(1)
x k3 xIA xEtOH TAEE K Eq(3)

(10) + (11)

xTAEE xH2 O rTAA = mr Q k1 xEtOH xTAA K Eq(1) xIA xH 2O k2 xTAA K Eq(2)

In this work, a non-equilibrium kinetic model is used to describe the reactions occurring in the reaction stages. TAEE is produced by the direct etherification
Table 1

Feed conditions and specification of a hybrid reactive distillation-pervaporation process

Feed conditions Column specification Pressure /kPa 101.3 Side stream flow rate/mols 1 1.5010
3

T/K 298

Flow rate /mols 1 2.7110

3

Mole fraction EtOH 0.5 TAA 0.5

Reaction stages 4

Stripping stages Total stages 8 A/m2 0.01 14

Column specification Side stream stage 2 Catalyst mass per stage/kg 0.125 Pressure/kPa 101.3 R 2 Qr/W 52

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rIA = rEtOH rTAA

(12) (13) (14)

rTAEE = rEtOH rH2 O = rTAA

where, k1 = exp(15.189 6597.3/T), k2 = exp(14.490 6372.9/T), k3 = exp(22.540 9184.6/T), KEq(1) = exp( 0.471 + 524/T), KEq(2) = exp(5.16 1824.3/T) and KEq(3) = exp( 5.64+2349/T).
3 3.1 SIMULATION RESULTS Standard condition

RD and RD-PV processes. It can be seen that when the PV is connected with the RD, the increase of TAEE mole fraction and the decrease of H2O mole fraction are observed. Therefore, it is obvious that the use of the PV unit can improve the efficiency of TAEE production. It should be noted here that since the side stream is drawn from the column at a low flow rate, a slight amount of water is removed from the system and thus a sudden change in the water concentration is not clearly observed.
3.2 Effect of side stream location

In this section, the performance of the hybrid RD-PV process and the conventional RD used in the synthesis of TAEE are compared to find out the improvement of the system performance with the use of the PV unit. In the standard condition, the PV is connected with the RD column which consists of only two sections (reaction and stripping sections). The flow rate of side stream to the PV unit is set to 0.0015 mols 1 and is drawn from the second stage of the RD column. The membrane area which is calculated from the amount of water needed to be separated from the side stream is 0.01 m2. The simulation results of both the processes are given in Table 2. It shows that when the PV unit is included in the TAEE process, the values of yield and selectivity of TAEE and conversion of TAA increase. Since the PV can remove more water from the process, the equilibrium-limited reactions [Eqs. (7) and (8)] are shifted to the product side, resulting in high consumptions of TAA and more generation of TAEE. It is noted that in the two RD processes, the distillate (LD) comprises mostly IA and a little amount of EtOH and H2O, whereas the residual (B) consists of mainly TAEE and H2O with unreacted TAA and EtOH. Fig. 3 shows the temperature profile and the mole fraction profile of TAEE and water in the
Table 2 Comparison of a conventional RD and a hybrid RD-PV process under the standard condition
Condition RD RD with pervaporation TAA TAEE conversion selectivity 69.56% 72.60% 81.59% 82.70% TAEE yield 56.76% 60.00% Mole fraction of TAEE in bottom 28.66 32.99

Figure 4 presents the effect of the location of side stream fed into the PV unit on TAA conversion and TAEE selectivity. It is found that when the location of the side stream changes from the upper stage to the lower stage, the conversion increases while the selectivity decreases. These results are particularly more pronounced when the side stream location is below the feed point. With the higher temperature of the side stream, more water can permeate through the membrane and consequently shift the reactions [Eqs. (7) and (8)] forward to more complete conversion. However, since the TAA dehydration is more pronounced, the selectivity and the yield of TAEE are decreased.

Figure 4 Effect of side stream location on the performance of the hybrid RD-PV process selectivity; yield; conversion

3.3

Effect of side stream flow rate

Figure 5 shows the result of changing the side stream flow rate to the conversion and selectivity. It can be seen that both the parameters are insensitive to the increased flow rate of the side stream. As the mole

Figure 3 Mole fraction and temperature profiles at the standard condition - - - temperature; mole fraction of TAEE in RD+PV; mole fraction of TAEE in RD; - - - mole fraction of H2O in RD+PV; - - - - mole fraction H2O in RD

Figure 5 Effect of side stream flow rate on the performance of the hybrid RD-PV process selectivity; yield; conversion

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fraction of water is still constant, independent on the flow rate, the permeation rate of water flowing through the pervaporation membrane, which depends on the mole fraction, is rather constant.
3.4 Reactive distillation with two pervaporation units

in the reactive distillation column is an important parameter determining the system performance. It is indicated that an optimal location of the pervaporation unit is at the reaction zone. The addition of more pervaporation units slightly improves the performance of the hybrid process.
ACKNOWLEDGEMENTS The supports from the Thailand Research Fund and the Commission on Higher Education are gratefully acknowledged. NOMENCLATURE
A D Fi H K ki LD L1 mr Pi Q Qr R ri T Tc xi membrane area, m2 total distillate flow rate (=LD+L1), mols 1 1 feed flow rate of component i, mols enthalpy equilibrium constant kinetic constant, mols 1 (mol H+) 1 1 liquid distillate flow rate, mols liquid flow rate to return from Stage 1 to Stage 2, mols 1 mass of dry ion-exchange resin, kg permeation rate of component i, mols 1m 2 + ion-exchange capacity (= 4.9), (mol H )(kg dry resin) 1 reboiler duty, W reflux ratio reaction rate, mols 1(kg dry resin) 1 temperature, K condenser temperature, K mole fraction of component i

Although the integration of the PV unit with the RD column provides an improved performance of TAEE production by a removal of water via the PV unit, high content of water in the column is still observed (Fig. 3). In this section, one more PV unit is added into the process in order to find out whether or not it can increase the efficiency of RD. From the results given in Table 3, it is found that the use of two PV units can increase the performance of RD, compared to that with only one PV unit. Moreover, the location of the second PV unit slightly affects the conversion and selectivity. However, it is observed that the suitable location for connecting PV units to the RD column is at the reaction zone (Stages 2-5).
Table 3 Effect of the use of two PVs on the performance of the hybrid RD-PV process
TAEE yield 60.02% 62.21% 62.69% 62.00% 61.98% 61.88% 61.69% Mole fraction of TAEE in bottom 0.3299 0.3659 0.3655 0.3569 0.3569 0.3565 0.3559

Side stream stage TAA TAEE of two conversion selectivity pervaporations 2 (one PV) 2,3 2,4 2,6 2,8 2,10 2,12 72.60% 75.45% 75.27% 74.64% 74.67% 74.98% 75.53% 82.70% 83.49% 83.34% 83.09% 83.05% 82.57% 81.71%

REFERENCES
1 2 Dai, C., Prospects on markets of MTBE and high octane numbers fuel additives, Advances in Fine Petrochemicals, 1, 37-43 (2000). Kitchaiya, P., Datta, R., Ethers from ethanol (2) Reaction equilibria of simultaneous tert-amyl ethyl ether synthesis and isoamylene isomerization, Ind. Eng. Chem. Res., 34, 1092-1101 (1995). Linnekoski, J.A., Krause, A.O.I., Rihko, L.K., Kinetics of the heterogeneously catalyzed formation of tert-amyl ethyl ether, Ind. Eng. Chem. Res., 36, 310-316 (1997). Chang, J. H., Yoo, J. K., Ahn, S. H., Lee, K. H., Ko, S. M., Simulation of pervaporation process for ethanol dehydration by using pilot test results, Korean. J. Chem. Eng., 15, 28-36 (1998). Sahapatsombud, U., Arpornwichanop, A., Assabumrongrat, S., Praserthdam, P., Goto, S., Simulation studies on reactive distillation for synthesis of tert-amyl ethyl ether, Korean. J. Chem. Eng., 22, 387-392 (2005). Aiouache, F., Goto, S., Reactive distillation-pervaporation hybrid column for tert-amyl alcohol etherification with ethanol, Chem. Eng. Sci., 58, 2456-2477 (2003).

CONCLUSIONS

The performances of a hybrid reactive distillation and pervaporation system for the synthesis of TAEE from the etherification of TAA and EtOH are analyzed in this study. The calculations are performed using the commercial software, Aspen Plus. It has been found that the proposed process can improve the efficiency of the TAEE production process by removing water from the system. The location of a pervaporation unit