Chemical Engineering and Processing 48 (2009) 10801087

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Chemical Engineering and Processing: Process Intensication

journal homepage: www.elsevier.com/locate/cep

Catalytic distillation for simultaneous hydrolysis of methyl acetate and etherication of methanol
Christina B. Dirk-Faitakis a , Weizhu An a , Tzong-Bin Lin b , Karl T. Chuang a,
a b

Department of Chemical & Materials Engineering, University of Alberta, Edmonton, Alberta, T6G 2G6, Canada CPC Corporation, Taiwan Chiayi, Taiwan

a r t i c l e

i n f o

a b s t r a c t
A catalytic distillation process was developed for the treatment of a methyl acetate/methanol byproduct stream typically encountered in polyvinyl alcohol manufacture. A two-step reaction scheme (hydrolysis + etherication) with separation is modeled in a catalytic distillation column to produce dimethyl ether (DME) and acetic acid. Simulations are performed using Aspen Plus and assume both physical and reaction equilibrium. A batch catalytic distillation test with only methyl acetate and methanol as feed, showed DME to be the sole distillate product, whereas, the bottoms product contained acetic acid, water, methanol, and DME. Simulation results show that this self-feeding reaction sequence can be used to produce a high purity DME product with complete conversion of water and methanol. The effect of pressure, water, molar feed ratio of methyl acetate/methanol, and feed location were examined. Even with no additional water fed, the hydrolysis reaction proceeds to completion and is only dependent on the molar feed ratio of methyl acetate/methanol. All possible azeotropes (methyl acetate/water, methyl acetate/methanol) are eliminated by completely reacting away water and methanol. 2009 Published by Elsevier B.V.

Article history: Received 7 February 2008 Received in revised form 6 March 2009 Accepted 6 March 2009 Available online 24 March 2009 Keywords: Catalytic distillation Hydrolysis Etherication Process modelling Simulation

1. Introduction Reactive distillation is a process that combines two unit operations, namely reaction and separation, into one unit. Heterogeneous catalysis reaction and multistage distillation can be carried out simultaneously in a single column, commonly referred to as catalytic distillation (CD). Catalytic distillation offers benets of reduced capital investment and also offers reductions in operating energy costs, especially for exothermic reactions. One of the classic processes that have seen signicant process improvements is the esterication reaction that produces methyl acetate. The underlying objectives in this process are to break the reactive azeotropes and produce a pure methyl acetate distillate product while at the same time achieving essentially complete conversion of the reactants [1]. Others have designed a catalytic distillation process for the purpose of removing dilute acetic acid from wastewater reactants [2]. In this case the dilute acetic acid reacts with methanol and the resulting product, methyl acetate, is removed from the top of the column. This process can save a large quantity of energy compared with conventional distillation.

Corresponding author at: Department of Chemical & Materials Engineering, University of Alberta, 536 CME Building, Edmonton, Alberta, T6G 2G6, Canada. Tel.: +1 780 492 4676; fax: +1 780 492 2881. E-mail address: karl.chuang@ualberta.ca (K.T. Chuang). 0255-2701/$ see front matter 2009 Published by Elsevier B.V. doi:10.1016/j.cep.2009.03.001

The reverse reaction to esterication is hydrolysis. The hydrolysis of methyl acetate in a CD column has also been investigated [3,4]. Ge et al. [4] examined the effect of the reux ratio on the conversion of methyl acetate for an equimolar feed of methyl acetate/water. They demonstrated an increase in methyl acetate conversion of 10% when compared to a xed-bed reactor under the same operating conditions. In the production of polyvinyl alcohol (PVA) methyl acetate (MA) is produced as a byproduct at a ratio of 1.68 ton of MA per ton of PVA. A typical hydrolysis section found in most PVA plants can contain four separation columns plus a xed-bed reactor [5,6]. Fuchigami [5] used catalytic distillation to hydrolyze methyl acetate back to methanol (MeOH) and acetic acid (AA) for reuse in PVA production. The total heat requirement of their optimized process was estimated to be about half that of the conventional hydrolysis process for a 4.1 molar excess feed ratio of water to methyl acetate. Xiao et al. [6] proposed replacing the xed-bed reactor by a catalytic distillation column to achieve 56% methyl acetate conversion, reportedly twice that of xed-bed reactor technology. In both processes additional water is fed to the catalytic distillation unit to achieve higher conversion of methyl acetate. The dehydration (etherication) of methanol to form dimethyl ether (DME) has been simulated in a catalytic distillation column [7]. Experimental kinetic data for the etherication of methanol was modeled using an Eley-Rideal mechanism and takes into account inhibition by water. Simulations showed that a high purity dimethyl ether product could be obtained for a 30-stage CD column operating at 0.91.0 MPa and a reaction zone between 126 and 138 C.

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Fig. 1. Self-feeding reaction scheme for combined hydrolysis and etherication.

The objective of this research was to examine the feasibility of using catalytic distillation in the conversion of a mixed methyl acetate/methanol feed at a near-azeotropic composition of 0.75:0.25 (mass fraction), typical to that found in PVA plants. The proposed process produces dimethyl ether and acetic acid through a two-step consecutive reaction scheme. The rst reaction involves the etherication of methanol to form dimethyl ether and water. The second reaction employs this water to react with methyl acetate in the hydrolysis reaction that produces methanol and acetic acid. The methanol produced during hydrolysis is then able to participate further in the etherication reaction to produce more water. In effect, the two reactions are self-feeding and can be visually represented as shown in Fig. 1. The benet of this catalytic distillation process is that no additional water is added as feed and the process continues as long as there is water and/or methanol in the column to react. Once the methyl acetate/methanol azeotrope has been broken, any further separation of methyl acetate and acetic acid becomes a matter of simple distillation. This process is advantageous over those previously proposed [5,6] as a reduction in the total number of reaction and separation columns would decrease capital costs. 2. Simulation modelling Simulations were performed using the Aspen Plus (Aspen Technology Inc., Aspen Plus , Version 2004.1, Cambridge, MA, 2005) software package. The catalytic distillation unit was modeled using the RadFrac operation in Aspen Plus . It uses the equilibrium stage model, also called the MESH model, and consists of a set of nonlinear equations to represent material balance, vaporliquid equilibrium, mole fraction summation, and heat balance. The reactions in the column were based on chemical equilibrium. The equilibrium constant was computed from Gibbs energies from the Aspen Plus database. 2.1. Physical equilibrium An important consideration in any catalytic distillation simulation is the choice of physical equilibrium model and the ability to reliably predict multicomponent vaporliquid equilibria (VLE) and liquidliquid equilibria (LLE). Reliable VLE and LLE are needed to establish distillation boundaries and to determine

if and where azeotropes and phase separations occur. There exists an abundance of patchwork/piecemeal phase equilibrium data in the open literature on the multicomponent mixture of methyl acetatemethanolwateracetic acid and its respective subsystems. The various equations used to model these systems include the Wilson, Van Laar, NRTL, UNIQUAC, and Margules, and usually take into account the non-ideality of the vapor phase (due to dimerization of acetic acid) by using either the Hayden-OConnell (HOC) or MarekStandart (MS) method. An additional component in our process is dimethyl ether and so an additional set of binary interaction parameters have to be determined. Considerable effort has been expended to try to bring together as much of the recent, readily accessible available data as possible to reconcile into one set of binary parameters. Previous simulation work in our lab with the methyl acetatemethanolwateracetic acid system has found that the NRTL equation suitably represents the data [2,8]. In this work the NRTL-HOC property method was used because of the presence of high concentrations of acetic acid. It is reported that the methyl acetatemethanol system exhibits an azeotrope at 0.677 mole fraction methyl acetate with a corresponding minimum boiling point of 54 C [9]. Gmehling and Blts [10] measured the azeoptrope at 53.5 C and 0.6618 mole fraction methyl acetate in the vapor at 101.32 kPa, and 0.6986 mole fraction methyl acetate at 52.87 kPa and 36.70 C. The binary VLE data of Bernatov et al. [11], Figurski and von Weber [12], and Nagata [13] as well as the high pressure T-xy data of Nagahama and Hirata [14] were simultaneously regressed to obtain NRTL binary interaction parameters. Methyl acetatewater exhibits a homogeneous azeotrope and also displays a miscibility gap in the region at ambient pressure. Agreda et al. [1] report a minimum boiling azeotrope at 95 wt.% methyl acetate at Taz = 56.1 C, whereas Bessling et al. [15] report a composition of 0.92 methyl acetate. The VLE data of [11,14], McKeown and Stowell [16], as well as the LLE data of Qiu et al. [17], were regressed to obtain NRTL binary interaction parameters. DMEmethanol binary interaction parameters were obtained by regressing the VLE data from Chang et al. [18], (up to 80 C), and Teodorescu and Rasmussen [19], and the LLE data of Park et al. [20]. DMEH2 O binary parameters were regressed from VLE data of Pozo and Streett [21], (up to 75 C), and Dahlhoff et al. [22], and LLE data of [20]. Binary interaction parameters for the following subsystems were taken from Aspen Plus data banks: MeOHH2 O, MeOHAA, MAAA, H2 OAA. No data bank values of the interaction parameters exist for the DMEMA or DMEAA systems and we were unable to locate any VLE in the open literature, so the Dortmund modied UNIFAC method was used to estimate these binary interaction parameters. After binary interaction parameters had been determined, the equilibrium model was used to construct ternary phase diagrams and these were compared to those found in the literature [17,20]. Table 1 summarizes the interaction parameters used in the prediction of equilibrium data.

Table 1 Summary of NRTL binary interaction parameters used in the prediction of equilibrium data. Component i MA MeOH MA MeOH MeOH MA WATER DME DME DME Component j MeOH DME WATER WATER AA AA AA WATER MA AA Temperature units K K K K K K K K K K aij 1.14353 8.062702 2.43297 2.626 3.8591 0 3.3293 0.96683 0 0 aji 0.509837 15.0667 0.12096 4.8241 7.4858 0 1.9763 0.825228 0 0 bij 536.8947 1659.63 1311.373 828.3871 975.377 415.2702 723.888 39.5507 290.545 689.3832 bji 31.74408 3836.088 805.9797 1329.54 2151.88 239.246 609.8886 67.57742 452.0198 431.568 cij 0.3 0.12748 0.419742 0.3 0.3 0.3 0.3 0.77735 0.3 0.3

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Table 2 Azeotropes predicted by Aspen Plus using the NRTL model. Azeotrope MAMeOH (homogeneous) P (MPa) 0.1 0.5 0.1 0.5 Taz ( C) 53.53 104.04 55.97 109.61 Component MA MeOH MA MeOH MA H2 O MA H2 O Mole fraction 0.6525 0.3475 0.5093 0.4907 0.8861 0.1139 0.8117 0.1883 Mass fraction 0.8127 0.1873 0.7058 0.2942 0.9697 0.0303 0.9466 0.0534

MAH2 O (homogeneous)

2.2. Chemical equilibrium The two concomitant reactions considered in the process are the hydrolysis of methyl acetate and the etherication of methanol. The hydrolysis of methyl acetate with water over an acid catalyst produces acetic acid and methanol: MA + H2 O AA + MeOH (1)

position remained constant over several hours. Vapor and liquid samples were measured on an HP 6890 GC equipped with a Poropak Q packed column and thermal conductivity detector. The GC conditions were as follows: Tinjector = 150 C; Toven = 50 C for 5 min, to 200 C at 30 C/min and held for 10 min; Tdetector = 200 C.

4. Results and discussion 4.1. Correlation and prediction of physical equilibrium data Fig. 2 shows the ternary phase diagram for MAMeOHH2 O at P = 101.3 kPa and T = 20 C and compares it with experimental data of Qiu et al. [17]. As can be seen from the gure, the NRTL model well represents the liquidliquid equilibria of the system. The singular points on the left and bottom axis in Fig. 2 also show the location (composition and temperature) of the two homogeneous azeotropes, namely methyl acetate/methanol and methyl acetate/water, and maps the distillation boundary for the system. Fig. 3 shows the ternary phase diagram for DMEMeOHH2 O at P = 911.9 kPa and T = 40 C predicted by Aspen Plus using the NRTL model and compares it to the experimental data of [20]. Both systems exhibit small regions of immiscibility. Prediction of the azeotropes by the simulation program is presented in Table 2. No ternary or higher order azeotropes were found.

The reaction is equilibrium limited with a reported equilibrium constant of 0.13 at 25 C [23]. The etherication of methanol, also commonly referred to as a dehydration reaction, consumes 2 mol of methanol to produce 1 mol of DME and 1 mol of water: 2MeOH DME + H2 O (2)

The equilibrium constant has been reported to range from 68.4 to 52.3 in the temperature range from 85 to 115 C [24]. The overall reaction equation is given by: MA + MeOH DME + AA (3)

Because water is both consumed and produced stoichiometrically, it drops out of the overall reaction equation. The temperature dependency on the equilibrium constant, Keq , is computed from Gibbs energies and this is taken into account by the Aspen Plus program. The constant is activity-based. An equilibrium model is used to investigate the feasibility of the proposed process design. The use of an equilibrium model does not explicitly assume that the reactions are instantaneous under the conditions of interest; rather, that a long enough residence time in the reaction zone of the CD column will be enough time for equilibrium to be reached. Continued simulation work will include kinetic data to size the CD column. 3. Batch catalytic distillation experiment To examine the reliability and effectiveness of the physical and reaction equilibrium models, a batch catalytic distillation simulation was performed and compared to experimental data collected in the lab. For the experimental test, a batch Parr reactor was loaded with a 150 g mixture of MA/MeOH feed in a 75:25 weight ratio MA, along with 19 g of previously dried acid catalyst (Amberlyst 35Wet, Rohm and Haas Company). The top of the reactor was modied with a stainless steel condenser, which allowed the vapor components to condense and reux back into the reactor. The condenser was cooled with cold water. The top of the condenser was tted with a valve. To maintain a constant pressure in the reactor the valve was periodically opened to allow the most volatile component (i.e., DME) to escape. Gas chromatograph (GC) analysis of the off-gas from the condenser conrmed that >99% DME was leaving the reactor. The reactor was operated at 120 C and 1.03 MPa over a period of 48 h until equilibrium had been reached. It was determined that equilibrium was established when the valve remained closed (i.e. no more DME formed), and based on a number of vapor and liquid samples from the reactor, that showed that the com-

Fig. 2. Ternary phase diagram for MAMeOHH2 O at P = 101.3 kPa and T = 20 C predicted by Aspen Plus using the NRTL model (open circles) and comparison to experimental data (lled circles) of Qiu et al. [17].

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Table 3 Liquid product composition for batch catalytic distillation experiment at equilibrium and simulation at T = 120 C and P = 1.03 MPa for MA/MeOH mass feed ratio of 75:25. Component Methyl acetate Methanol Dimethyl ether Water Acetic acid
a

Simulation Product stream (P2), wt.% 58.5 2.1 9.8 4.0 25.7

Experimental product stream, wt.% 61.4 2.87 7.08 5.12 23.5

Corrected exptl. product stream, wt.% 59.62 2.79 9.80a 4.97 22.82

Experimental data has been renormalized to the simulation data for DME.

4.2. Model batch catalytic distillation The steady state Aspen Plus program was used to model the state of the batch catalytic distillation process once it had reached equilibrium. Batch catalytic distillation is an unsteady state process with the pressure and product composition changing over time. However, if DME is allowed to escape as it is being produced (in order to maintain constant pressure in the reactor), then a steady state simulation can be performed once reaction equilibrium has been established. At this point no more reaction occurs and the pressure and composition of the products remains constant. A twostage equilibrium reactor with distillation column was sufcient to model the process and is shown schematically in Fig. 4. The feed stream (F) is the reactants at the start of the reactive distillation experiment and the product stream (P2) is the liquid phase at the end of the batch catalytic distillation (i.e. at equilibrium). Since the vapor ow (V2) in the simulation is zero, no additional distillation column is required. Table 3 shows the liquid composition for the batch catalytic distillation simulation and compares it to experimental batch catalytic distillation results. The simulation and experimental results compare well except for the amount of dimethyl ether present in the liquid phase. The simulations predict 10 wt.% of the liquid phase is DME. The liquid samples taken from the reactor were injected at ambient pressure. It is likely that some of the DME from the experimental liquid samples was lost due to ashing as DME is a gas at ambient temperature and pressure. In order to account for the DME lost from the liquid samples an attempt was made to renormalize the composition based on the

Fig. 4. Aspen Plus two-stage equilibrium reactor with distillation column used to model the batch distillation process.

assumption that the liquid phase DME composition determined from the simulation is correct. The corrected composition of the product stream is also found in Table 3. From the batch catalytic distillation experiment it was demonstrated that both hydrolysis and etherication reactions occur, since both acetic acid (hydrolysis) and dimethyl ether and water (etherication reaction) are present as components in the product stream. It was also demonstrated that both reactions proceed without any initial water present in the feed. We have shown that the catalyst is active for both reactions in the presence of the reaction mixtures. Furthermore, it can be seen that the equilibrium model sufciently describes the phenomena of combined reaction and separation for the case of batch catalytic distillation for the simultaneous hydrolysis of methyl acetate and etherication of methanol. 4.3. Simulation of continuous catalytic distillation column The continuous catalytic distillation process consists of a 20stage CD column with total condenser and partial reboiler. The parameters for the base case simulation are given in Table 4. All feed streams enter at 25 C. 4.3.1. Effect of pressure Operating pressure is one of the key elements in the design of a CD column. The choice of operating pressure for a catalytic distillation column depends on many considerations such as the overhead temperature, bottom temperature, reaction temperature and relative volatilities of the components in the system. The col-

Fig. 3. Ternary phase diagram for DMEMeOHH2 O at P = 911.9 kPa and T = 40 C predicted by Aspen Plus using the NRTL model (open circles) and comparison to experimental data (lled circles) of Park et al. [20].

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Table 4 Parameter values for the base case used in the simulations. Parameter Column pressure (MPa) Distillate to feed ratio (D/F) Reux ratio (RR) Total number of stages Reaction stage location Feed stage location (above stage) Feed composition (mass basis) MA MeOH H2 O Value 0.5 0.45 2.1 20 316 (inclusive) 12 0.75 0.23 0.02

umn pressure sets the lower and upper bounds of the temperature within the column. For the process to be economic, the operating pressure should be chosen within a range such that water can be used as a coolant for the overhead condenser and steam can be used as a heating medium for the reboiler. Within this range, the reaction temperature mainly determines the operating pressure. Because chemical reactions take place within the liquid phase, the reaction temperature is close to the boiling point of liquid owing around the catalyst. As a result the reaction temperature increases with column pressure. Generally, the maximum temperature of the catalyst limits the pressure in the column. Fig. 5 shows the effect of column pressure on the temperature in the column. In these simulations the parameters are those as in the base case, except for the reux ratio. As column pressure was increased, the reux ratio was also increased concurrently in order to achieve mathematical convergence in the simulation. There are two factors that may affect convergence: One is the separation factor for vaporliquid equilibrium, and the second is the reaction equilibrium. By changing the pressure these two parameters may fall outside the operable range of the CD column and the calculations will not converge. Therefore, the reux ratio was increased by the minimum amount that would satisfy convergence of the CD column, with all other parameters being held constant. Since the suggested maximum operating temperature for Amberlyst 36 is 150 C, a maximum operating pressure of 0.5 MPa is recommended. 4.3.2. Effect of water The amount of water in the feed is an important variable in the CD process because water is a necessary reactant in the hydrolysis reaction. However, water is also produced via the etherication reaction. Therefore, there should be an optimum amount of water that will allow both reactions to proceed readily without accumulating a large amount of water byproduct. The optimum process should achieve maximum conversion of reactants while at the

Fig. 6. Effect of excess water (0.04 mass fraction of the feed) on product distribution in the CD column.

same time completely removing water from any of the product streams. Fig. 6 shows the effect of excess water content of the feed stream (relative ratio of MA:MeOH in the feed remains constant). When the water content of the feed has a mass fraction of 0.04, the hydrolysis reaction is now limited by methyl acetate. Methyl acetate is completely consumed and excess water exits with acetic acid in the bottoms product. Conversely, when no water enters in the feed, only the water that is produced through methanol etherication is available for the hydrolysis reaction. In this case DME is still the distillate product, but a mixture of acetic acid and methyl acetate is now the bottoms product. All of the water and methanol is reacted away. This CD column prole is shown in Fig. 7. For this case, if the D/F ratio is reduced from 0.45 to 0.414 a distillate DME purity of 99.8 wt.% can be reached. 4.3.3. Effect of methyl acetate/methanol feed ratio Based on the overall reaction equation given by Eq. (3), the effect of the molar feed ratio of methyl acetate to methanol on the process appears straightforward. Increasing either methanol or methyl acetate in the feed should favour DME and AA product formation in equimolar amounts. However, based on the stoichiometry of the individual reactions, this is not necessarily true. The effect of increasing the methyl acetate/methanol feed ratio results in complete conversion of water and methanol in the CD column with a prole similar to Fig. 7. If considering only the hydrolysis reaction, one would expect that by increasing the amount of

Fig. 5. Effect of pressure on the temperature prole in the CD column.

Fig. 7. Effect of no water in the feed on product distribution in the CD column.

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Fig. 8. Effect of stoichiometric limited MA/MeOH feed = 0.55; RR = 1.8, D/F = 0.475, all other parameters as in Table 4.

Fig. 9. Effect of feed stage location (stage 3) on concentration prole in the CD column.

methyl acetate in the feed, water could be more easily reacted to completion. When water is consumed and methanol is produced the equilibrium for the etherication also shifts to the production of DME. When the methyl acetate/methanol feed ratio decreases below a specic stoichiometric amount, the methyl acetate reactant becomes the limiting reactant. Simulation results show that column parameters can be varied to completely remove methyl acetate and methanol from the column, but water and acetic acid remain as the bottoms product. This is shown in Fig. 8 for a methyl acetate/methanol molar feed ratio of 0.55. The reux ratio is 1.8, the D/F = 0.475, and all other parameters are as in Table 4. Based on the overall reaction equation (3), it is also theoretically possible to design a process that gives 100% conversion of methanol and methyl acetate when fed in a 1:1 molar ratio. It has already been shown in Section 4.3.2 that no additional water needs to be added to the process in order for the reactions to proceed. With the same column conditions as given in Table 4, a D/F ratio = 0.5, RR = 4, molar feed ratio of methyl acetate/methanol = 1, and no additional water fed to the column, pure DME and acetic acid are the only products. At these conditions a DME distillate of 99.5 wt.% purity and an acetic acid bottoms product of 99.5 wt.% purity are obtained. 4.3.4. Effect of feed location In traditional distillation column design, the optimum feed stage is determined so as to minimize the total number of stages required. In a catalytic distillation column, however, it is desirable to locate the feed stream on or near the reaction stage(s) where the reactant concentrations are maximum in order to facilitate the chemical reactions. Figs. 9 and 10 show column proles for a feed location of 3 and 16, respectively. These represent the top and bottom of the reaction zone. As has been shown previously [25], for the catalytic distillation of ethanol/water with isobutylene, it is preferred that the heavier liquid feed enters within or above the reaction zone in the column, whereas the lighter feed, isobutylene, does not have a signicant effect on the reaction within the column. In this case there is only one mixed feed that enters the column. When the methyl acetate/methanol feed enters at stage 3 (Fig. 9), the feed will ow downwards into the reaction zone and complete conversion of methanol and water is achieved. This is because both methanol and water are heavier than methyl acetate. When the feed enters at stage 16 (Fig. 10), most of the liquid feed bypasses the reaction zone; as methyl acetate has a lower boiling point compared to methanol (56.94 C vs. 64.7 C), it tends to travel up the column, whereas methanol and water will slip out the bottom of the column before having a chance to react.

4.4. Simulation of catalytic distillation process for DME and acetic acid The process owsheet for the production of high purity dimethyl ether and acetic acid via a two-step reaction and separation in a catalytic distillation column is shown in Fig. 11. Table 5 shows the parameters for the process simulation. The values for the CD column for pressure, D/F ratio and total stages were taken from Table 4, and values for reux ratio, feed and reaction stage locations were chosen to achieve a high-purity DME distillate (99.99 wt.%) with complete removal of water. The mixed methyl acetate/methanol/water feed (F) enters the catalytic distillation (CD) column at stage 6

Fig. 10. Effect of feed stage location (stage 16) on concentration prole in the CD column.

Fig. 11. Process ow diagram for the production of high purity DME and acetic acid.

1086 Table 5 Parameters for the process simulation. Parameter Catalytic distillation (CD) Column pressure (MPa) Distillate to feed ratio (D/F) Reux ratio (RR) Total number of stages Reaction stage location Feed stage location (above stage) Feed composition (mass basis) MA MeOH H2 O Distillation (D) Column pressure (MPa) Distillate to feed ratio (D/F) Reux ratio Total number of stages Feed stage location (above stage)

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Value 0.5 0.45 1.4 20 616 (inclusive) 6 0.75 0.23 0.02

the bottoms product contained acetic acid, water, methanol, and dimethyl ether as predicted based on chemical equilibrium calculations (simulations). From the continuous column simulation results it can be concluded that the water concentration as well as the molar feed ratio of methyl acetate/methanol have a signicant inuence on the operation of the column and will effect the nal product distribution. With minimum water in the feed and a stoichiometric excess of methyl acetate, all water and methanol can be removed, resulting in a pure dimethyl ether distillate and a mixed methyl acetate/acetic acid bottoms product, which can be further separated through simple distillation. Even with no additional water fed to the column, the process is able to produce a high purity dimethyl ether distillate (99.8 wt.%) and mixed methyl acetate/acetic acid bottoms product.

0.1 0.069 10.5 10 6

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Fig. 12. Concentration prole in the CD column of Fig. 11; simulation parameters from Table 5. Table 6 Composition of process streams depicted in Fig. 11 (mole fraction), based on simulation parameters from Table 5. Component F DME MA MeOH WATER AA 0.0000 0.5499 0.3898 0.0603 0.0000 B 0.0000 0.0722 0.0001 0.0002 0.9275 Stream P1 0.9999 0.0000 0.0000 0.0000 0.0000 P2 0.0000 0.9906 0.0007 0.0013 0.0073 P3 0.0000 0.0042 0.0000 0.0001 0.9957

at the top of the reaction zone. The distillate from the CD column is a high purity dimethyl ether product (P1); the bottoms from the CD column (B) is fed to the distillation (D) column and results in high purity methyl acetate (P2) and acetic acid (P3). Fig. 12 shows the concentration proles in the catalytic distillation column. A summary of the stream compositions is provided in Table 6. 5. Conclusions It was concluded that the combined hydrolysis and etherication reactions can proceed co-currently in a CD column to produce both dimethyl ether and acetic acid. Batch catalytic distillation tests showed dimethyl ether to be the sole distillate product, whereas,

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