Article pubs.acs.org/IECR
Transesterification of Methyl Acetate with n‑Propanol: Reaction Kinetics and Simulation in Reactive Distillation Process Lanlan Shen, Lei Wang, Hui Wan,* and Guofeng Guan* State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, People’s Republic of China S Supporting Information *
ABSTRACT: The reaction kinetics of the transesterification of methyl acetate with n-propanol is described by pseudohomogeneous (PH) kinetic model, which can successfully correlate with the experimental data. The influence of temperature as well as catalyst loading and initial molar ratio of n-propanol to methyl acetate on this reaction is studied under the condition of eliminating both internal and external mass transfer resistances. On the basis of the PH kinetic model, the influences of design parameters are studied, such as recycle flow rate, the number of stages of the reactive distillation column (RD), and theoretical stages of the conventional distillation column. These parameters are further optimized to minimize total annual cost in the RD process.
1. INTRODUCTION A large quantity of methyl acetate is produced during the synthesis of polyvinyl alcohol (PVA) and purified terephthalic acid (PTA). For example, 1.5−1.7 tons of methyl acetate are produced as byproduct for every ton of PVA.1 Because of its low industrial application, methyl acetate ought to be converted into other valuable chemicals. For example, acetic acid and methanol are products of methyl acetate hydrolysis, but the high energy consumption is a big concern. Comparatively, transesterification of methyl acetate with n-propanol is more attractive since the product methanol is a useful raw material and n-propyl acetate can be used as organic solvent. Until now, only the transesterification kinetics of methyl acetate with n-butanol or hexanol catalyzed by Amberlyst15,2−4 NKC-9,5 ionic liquid,6 and Amberlyst-1317 have been reported, and the pseudohomogeneous (PH) model has been proved to be in good agreement with experimental data. Thus, it is desirable to investigate the reaction kinetics of transesterification of methyl acetate with n-propanol. Reactive distillation (RD) has obtained great attention as replacement for many conventional processes, especially for equilibrium limited reactions. RD provides efficient path to improve conversion, increase selectivity, and reduce costs by removing the products away from reaction mixture. It has been applied to overcome the chemical limitation of transesterification of methyl acetate with n-butanol. For the production of n-butyl acetate, different processes with two, three, or four columns have been investigated in many papers,8−13 from which it can be concluded that the improved process consisting of only two columns, namely the RD process in this work, provides much less capital cost than other processes. This work presents the transesterification of methyl acetate with n-propanol using Amberlyst-15 as catalyst, which has not been reported before. First, kinetic experiments are performed and the effects of temperature, catalyst loading, and initial molar ratio of n-propanol to methyl acetate are investigated. Then PH model is adopted to describe the reaction rate. Finally, an equilibrium-stage model is employed for the © 2014 American Chemical Society
simulation of the RD process, which includes an RD column and a conventional distillation column. The design parameters, such as recycle flow rate, the number of stages of the reactive distillation column, and theoretical stages of the conventional distillation column, are also optimized.
2. EXPERIMENTAL SECTION 2.1. Material and Catalyst. n-Propanol (>99.0 wt %), methanol (>99.5 wt %), methyl acetate (98.0 wt %), and n-propyl acetate (98.5 wt %) were purchased from Sinopharm Chemical Reagent Co. Ltd. and used without further purification. Macroreticular ion-exchange resin Amberlyst-15 purchased from Rohm and Haas was used as catalyst. Amberlyst-15 was washed several times by distilled water and dried at 353.15 K until the mass remained constant before use. 2.2. Procedure. The experiments were carried out in a 500 mL three-neck round bottomed flask equipped with water bath, mechanical stirrer, water-cooling condenser, and thermometer. Desired amount of methyl acetate and catalyst were successively added into the flask. When the temperature reached the desired value, n-propanol was charged into the mixture. Then time measurement and stirring were started immediately. It usually took 24 h every experiment and about 20 liquid samples were taken. 2.3. Analysis. The samples were analyzed by a gas chromatography instrument (SP6800A) equipped with a capillary column (OV1701 30 m × 0.32 mm ×0.5 μm) and a flame ionization detector (FID). N2 was used as the carrier gas. The temperature of the injector, detector, and oven were set at 373.15, 373.15, and 353.15K, respectively. 3. RESULTS AND DISCUSSION 3.1. Calculation of Activities and Thermodynamic Properties. The activity coefficients are taken into account for the real behavior of liquid phase. In the reaction of transesterification Received: Revised: Accepted: Published: 3827
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of methyl acetate with n-butanol or hexanol, UNIQUAC,3,4,7 NRTL,2 and UNIFAC5,12,14 models are applied for calculating the activity coefficients. Thermodynamic properties for simulation in the RD process are determined by the UNIQUAC model.15−17 In the present work, the UNIQUAC model is chosen for calculating activity coefficients and thermodynamic properties. 3.2. Reaction Kinetic Model. 3.2.1. Absence of Mass Transfer Resistance. All experiments should be carried out under conditions eliminating the influence of mass transfer resistance when calculating reaction kinetics. The Weisz-Prater criterion is usually used to determine the effect of intraparticle mass transfer on the reaction. The modulus value in our study is 4.8 × 10−4, which is much smaller than 0.1, indicating the influence of intraparticle mass transfer is negligible. This conclusion is also confirmed by different esterification and transesterification reactions using Amberlyst-15 catalyst.4,18−20 For excluding external diffusion, the effect of stirrer speed varied between 100 to 500 rpm are studied, and the reaction rate keeps constant after the stirrer speed reaches 200 rpm Therefore, all the further experiments are carried out under the stirrer speed of 300 rpm. This observation is also verified by the work of Popken.18 3.2.2. Effect of Catalyst Loading. Figure 1 shows the effect of catalyst loading on the forward reaction rate constant at
Figure 2. The effect of different initial molar ratio of n-propanol to methyl acetate on conversion of methyl acetate at 328.15 K and catalyst loading of 10 wt %.
Figure 3. The relationship between the conversion of methyl acetate and reaction temperature (catalyst loading of 10 wt % and initial molar ratio of n-propanol to methyl acetate being 1).
Figure 1. The effect of catalyst loading on the forward reaction rate constant at 328.15 K and initial molar ratio of n-propanol to methyl acetate being 1.
to 333.15 K. The conversion of methyl acetate increases rapidly with elevated temperature, but the equilibrium conversion of methyl acetate is nearly the same in the range of temperatures studied. A similar conclusion is also drawn by various transesterification reactions using different solid catalysts, which is ascribed to the small heat of transesterification reactions.4,5,7 3.2.5. PH Kinetic Model and Chemical Equilibrium. Most acidic resin catalyzed esterification and transesterification reactions are classified as quasi-homogeneous reactions. The second-order PH model applied for esterification and transesterification reactions is in good agreement with experimental data.2−5,23−26 In this work, the reaction rate is expressed as a PH model:
328.15 K and initial molar ratio of n-propanol to methyl acetate being equal to l. It is obvious that the reaction rate constant increases linearly with the addition of catalyst loading. The relationship between reaction rate constant and dry catalyst mass can be expressed as k0 = 2.68 × 10−4mcat. Such behavior is due to the increased amount of acidic sites for the reaction with the addition of catalyst loading.21,22 3.2.3. Effect of Molar Ratio of n-Propanol to Methyl Acetate. The experiments are carried out at the initial molar ratio of n-propanol to methyl acetate varying from 1.25:1 to 1.5:1, while other operating variables are kept unchanged. The effect of molar ratio of alcohol to ester on the conversion of methyl acetate is shown in Figure 2. It should be noted that the conversion of methyl acetate is further increased with the growing of the initial molar ratio. When the molar ratio increases from 1.25:1 to 1.5:1, the increment of equilibrium conversion is about 10%. 3.2.4. Effect of Reaction Temperature. The effect of reaction temperature on conversion is shown in Figure 3, which is conducted under the temperature ranging from 313.15 K
1 1 dni = k+1aA aB − k −1aCaD mcat vi dt ⎛ ⎞ 1 = k+1⎜aA aB − aCaD⎟ ⎝ ⎠ K
r=
K= 3828
k+1 k −1
(1)
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Where r is reaction rate, kmol·s−1·kg‑1 cat; mcat is the mass of catalyst, kgcat ; νi is stoichiometric coefficient; k+1, k−1 are constants of forward and reverse reactions, respectively, kmol· s−1·kg−1 cat ; aA , aB , aC , and aD, are activities of methyl acetate, n-propanol, n-propyl acetate and methanol, respectively; K is chemical equilibrium constant. The values of k+1 and k−1 depending on temperature can be expressed as Arrhenius equations: ln k+1 = ln k+0 1 +
−E+1 RT
ln k −1 = ln k −01 +
− E −1 RT
k0+1
(3)
(4)
k0−1
where and are pre-exponential factors for forward and reverse reactions, respectively, kmol·s−1·kg−1 cat ; and E+1 and E−1 are the forward and reverse activation energy, respectively, kJ·mol−1. The fourth-order Runge−Kutta method is used for estimating the above parameters. The objective function is the minimization of sum of the residual squares (SRS) between experimental and calculated mole fractions of methyl acetate. The parameters of k0+1 and k0−1 are obtained from the liner relationship of Arrhenius plots (Figure 4) and listed in Table 1
Figure 5. RD process of methyl acetate transesterification system.
methanol with composition of 66.57 mol % methyl acetate at 326.87 K, and the other is n-propanol and n-propyl acetate with the composition of 63.72 mol % n-propanol at 367.99 K. Hence, the order of the normal boiling point temperature for the quaternary system is as follows: n‐propyl acetate > n‐propanol > n‐propanol /n‐propyl acetate > methanol > methyl acetate > methyl acetate/methanol
The simulation of RD column is based on an equilibrium-stage model that is used for solving the MESH and reactive equations.27,28 n-Propanol and methyl acetate flows are with same rate of 50 kmol/h. At the reaction section, the assumption of residence time is 5 min, and the bulk catalyst density is 770 kg/m3. Column pressure drop is assumed to be 0.3 atm when column is operated at 1 atm with condenser being stage 1 and reboiler being stage N. n-Propyl acetate with purity of 99.5 mol % is taken from the bottom of RD column by adjusting the heat duty, while overhead product rich with methanol is fed into the second column for further purification. Additionally, purity of methanol is set to 99.5 mol % in the bottom flow of second column. Meanwhile, the top flow of second column with mixture of methanol and methyl acetate is recycled to the RD column. 3.3.1. Effects of Operation Parameters in the RD Process. 3.3.1.1. Recycle Flow Rate. The recycle flow from the top of the second column to the RD column is one of the key factors in the RD process. The increasing recycle flow rate will increase the amount of methyl acetate fed into the RD column, which is favorable to the transesterification reaction, thus less number of theoretical stages is needed. Low investment of RD column is required when recycle flow rate is high, but energy consumption also increases. As shown in Figure 6, the number of theoretical stages of RD column decreases fast with the increasing of recycle flow rate at first, but this tendency slows down as the recycle flow rate further increases. Consequently, the recycle flow is recommended as 150 kmol/h.
Figure 4. Arrhenius plot for forward and reverse reactions.
with average errors around 2%. It is demonstrated that the PH model provides very good predictive capabilities. Chemical equilibrium constants calculated from experiments, illustrate slight change over temperatures. The relationship of ln K with 1000/T is obtained and displayed by eq 5. 767.5 (5) T 0 The standard enthalpy of reaction ΔHr established from Van’t Hoff equation is 6.380 kJ/mol, which agrees with anticipation for an endothermic reaction. 3.3. Simulation. Before describing the RD process (Figure 5) with a RD column and a conventional distillation column (namely the second column) in detail, it is necessary to study the phase behavior of this system. Two binary minimum boiling azeotropes exist under atmospheric pressure. One is methyl acetate and ln K = 1.813 −
Table 1. Parameters of PH Model Correlated from Experimental Data the pre-exponential factor k0 (kmol·s−1·kg−1 cat ) activation energy E (kJ·mol−1)
forward reaction
reverse reaction
461.66 ± 9.23 49.05 ± 0.93
74.97 ± 1.50 42.66 ± 0.81
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Figure 6. The relationship between the number of theoretical stages and recycle flow rate in RD column.
Figure 8. The effect of the number of rectifying stages on the conversion of methyl acetate in RD column.
3.3.1.2. Number of Stripping Stages. The effect of the number of stripping stages on the transesterification is investigated in this part. As shown in Figure 7, the conversion
Figure 9. The effect of the number of reactive stages on the conversion of methyl acetate in RD column.
no longer increases significantly when the number of reactive stages reaches 36. Consequently, the number of reactive stages is recommended as 36. 3.3.1.5. Reflux Ratio of RD Column. The conversion of methyl acetate is taken into account for the optimization of reflux ratio value of the RD column. The influence of reflux ratio on the conversion of methyl acetate is shown in Figure 10. The conversion of methyl acetate increases quickly when the reflux ratio increases from 1.8 to 2.2. However, this tendency almost ceases when the reflux ratio is above 2.2. Consequently, the reflux ratio is recommended as 2.2. 3.3.1.6. Theoretical Stages of the Second Column. Under atmosphere pressure, the relationship between the number of theoretical stages and reflux ratio of the second column is studied (as shown in Figure 11). The number of theoretical stages declines with the increasing of reflux ratio, but this trend slows down when the reflux ratio exceeds 1.7. Consequently, the number of theoretical stages is recommended as 20. 3.3.2. Steady State Design. From the above study, number of reactive stages, stripping stages, and rectifying stages in RD column are chosen as 36, 8, and 37, respectively. The number of theoretical stages of the second column is 20 with feed stage of 14. These parameters are used as the initial value for steady state design. To obtain the optimum design parameters, it is vital to minimize total annual cost (TAC),29−33 which is defined as follows:
Figure 7. The effect of the number of stripping stages on the conversion of methyl acetate in RD column.
of methyl acetate increases with the addition of the number of stripping stages. The growing number of stripping stages will decrease the concentration of n-propyl acetate in the reactive section, which is favorable to the conversion of methyl acetate. When the number of stripping stages is above 8, the raising of conversion is not notable. Consequently, the number of stripping stages in the RD column is recommended as 8. 3.3.1.3. Number of Rectifying Stages. The effect of the number of rectifying stages on conversion of methyl acetate in RD column is shown in Figure 8. It is demonstrated that the conversion of methyl acetate rises with the growing number of rectifying stages, which is attributed to the decreasing concentration of methanol in the reactive section. The conversion of methyl acetate reaches 99% as the number of rectifying section increases to 37. Consequently, the number of stages in the rectifying section is recommended as 37. 3.3.1.4. Number of Reactive Stages. The n-propanol steam is fed at the top of reactive section, while the methyl acetate steam is fed at the bottom. The effects of the number of reactive stages on the conversion of methyl acetate and energy consumption of the RD column have been investigated. As shown in Figure 9, the conversion of methyl acetate increases with the growing number of reactive stages, which is due to the prolonging of residence time. The conversion of methyl acetate
TAC = operating cost + 3830
capital cost payback year
(6)
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Figure 10. The effect of reflux ratio on the conversion of methyl acetate in RD column.
Figure 12. Effects of design parameters on the TAC in RD column (FR = 146.75 kmol/h: (A) number of stripping stages and rectifying stages; and (B) number of rectifying stages and reactive stages). Figure 11. The relation between the number of theoretical stages and reflux ratio of the second column.
where payback period is assumed as 3-year. In the process, design parameters such as recycle flow rate (FR), the number of stripping stages (NS), the number of rectifying stages (Nr), and the number of reactive stages (Nrxn) in RD column, the number of theoretical stages in the second column (NT), are specified. The optimum design procedure is shown as follows: (1) Fix recycle flow rate (FR). (2) Set a number of reactive stages (Nrxn) in RD column. (3) Set a number of rectifying stages (Nr) in RD column. (4) Set a number of stripping stages (NS) in RD column. (5) Change the feed locations of RD column, and then vary reflux ratio and heat input until purity of n-propyl acetate is reached. (6) Go back to (4) and vary NS until the TAC is minimized. (7) Go back to (3) and change Nr until the TAC is minimized. (8) Go back to (2) and change Nrxn until the TAC is minimized. (9) Guess a number of theoretical stages in the second column (NT). (10) Change feed location in the second column, and then vary reflux ratio and heat input until desired purity of methanol is achieved. (11) Go back to (9) and change NT until the TAC is minimized. (12) Go back to (1) and change FR until the total TAC is minimized. The effects of the number of rectifying stages (Nr), stripping stages (NS), and reactive stages (Nrxn) on the TAC are shown in Figure 12, which reveals that the number of reactive stages
Figure 13. The effect of the number of theoretical stages on the TAC under optimum feed location in second column.
(Nrxn) is more sensitive than that of rectifying stages (Nr) and stripping stages (NS). Also, the area with large concentration of reactants is chosen for reaction section to facilitate the forward reaction. Consequently, the number of reactive stages (Nrxn) plays a dominant role in minimizing TAC. The number of reactive stages, rectifying stages and stripping stages in the RD column are recommended as 34, 40, and 9, respectively. The effect of the number of theoretical stages in the second column on the TAC is shown in Figure 13. It displays a minimum TAC when the number of theoretical stage of the second column is 27. For the recycle flow rate (FR), Figure 14 demonstrates a minimum total TAC when the recycle flow rate 3831
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Figure 14. The effect of recycle flow rate on the TAC in the RD process.
Figure 16. Liquid composition profile (A) and temperature distribution (B) in the second column.
and temperature distribution of the second column. The top product is mixture of methanol and methyl acetate near azeotrope composition, and the bottom product is high purity of methanol with temperature of 337 K.
4. CONCLUSIONS n-Propyl acetate and methanol with 99.5 mol % purity are obtained by transesterification of methyl acetate with npropanol from reactive distillation process. The reliable PH kinetic model with a second-order expression agrees well with experimental data. The activation energies for forward and reverse reaction are 49.05 and 42.66 kJ/mol, respectively. On the basis of the minimization of TAC, design parameters of the RD process are determined. The number of stripping stages, rectifying stages, and reactive stages in the RD column are optimized as 9, 40, and 34, respectively. The number of theoretical stages in the second column is 27 with a feed stage of 19. It is also found recycle flow is a dominant parameter in the RD process and optimized as 146.75 kmol/h.
Figure 15. Liquid composition profile (A) and temperature distribution (B) in the RD column.
is 146.75 kmol/h. It is the balance of the RD cost and the second column cost. The RD cost decreases with the increasing of the recycle flow due to the growth of reactants concentration, but the second column cost increases for higher feed flow rate, which means the recycle flow rate (FR) is a dominant design parameter. The RD process is optimized by adjusting the above parameters and the optimum results are summarized in the Supporting Information. Figure 15 provides composition profile and temperature distribution in the RD column. The area with large concentration of reactants is chosen for reaction section to facilitate the forward reaction. The maximum temperature in the reaction section is around 364 K, which is below the maximum operating temperature of catalyst. Figure 16 shows composition profile
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ASSOCIATED CONTENT
S Supporting Information *
The cost models and the computing method of TAC and optimum results of RD process. This material is available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*Phone: 86-25-83587198. E-mail:
[email protected] (W.H.);
[email protected] (G.G.F.). 3832
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Notes
(16) Steinigeweg, S.; Gmehling, J. Transesterification Processes by Combination of Reactive Distillation and Pervaporation. Chem. Eng. Process. 2003, 43, 447. (17) Resa, J. M.; Gonzalez, C.; de Landaluce, S. O.; Lanz, J. VaporLiquid Equilibrium of Binary Mixtures Containing Methanol + Propyl Acetate, Methanol + Isopropyl Acetate, Vinyl Acetate + Propyl Acetate, and Vinyl Acetate + Isopropyl Acetate at 101.3 kPa. J. Chem. Eng. Data 2001, 46, 1338. (18) Popken, T.; Gotze, L.; Gmehling, J. Reaction Kinetics and Chemical Equilibrium of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with Methanol and Methyl Acetate Hydrolysis. Ind. Eng. Chem. Res. 2000, 39, 2601. (19) Gao, X.; Li, X.; Li, H. Hydrolysis of Methyl Acetate via Catalytic Distillation: Simulation and Design of New Technological Process. Chem. Eng. Process. 2010, 49, 1267. (20) Pappu, V. K. S.; Yanez, A. J.; Peereboom, L.; Muller, E.; Lira, C. T.; Miller, D. J. A Kinetic Model of the Amberlyst-15 Catalyzed Transesterification of Methyl Stearate with n-Butanol. Bioresour. Technol. 2011, 102, 4270. (21) Ali, S. H.; Merchant, S. Q. Kinetics of the Esterification of Acetic Acid with 2-Propanol: Impact of Different Acidic Cation Exchange Resins on Reaction Mechanism. Int. J. Chem. Kinet. 2006, 38, 593. (22) JagadeeshBabu, P. E.; Sandesh, K.; Saidutta, M. B. Kinetics of Esterification of Acetic Acid with Methanol in the Presence of Ion Exchange Resin Catalysts. Ind. Eng. Chem. Res. 2011, 50, 7155. (23) Orjuela, A.; Yanez, A. J.; Santhanakrishnan, A.; Lira, C. T.; Miller, D. J. Kinetics of Mixed Succinic Acid/Acetic Acid Esterification with Amberlyst 70 Ion Exchange Resin As Catalyst. Chem. Eng. J. 2012, 188, 98. (24) Tao, D. J.; Wu, Y. T.; Zhou, Z.; Geng, J.; Hu, X. B.; Zhang, Z. B. Kinetics for the Esterification Reaction of n-Butanol with Acetic Acid Catalyzed by Noncorrosive Brønsted Acidic Ionic Liquids. Ind. Eng. Chem. Res. 2011, 50, 1989. (25) Ju, I. B.; Lim, H. W.; Jeon, W.; Suh, D. J.; Park, M. J.; Suh, Y. W. Kinetic Study of Catalytic Esterification of Butyric Acid and n-Butanol over Dowex 50Wx8−400. Chem. Eng. J. 2011, 168, 293. (26) Kolah, A. K.; Asthana, N. S.; Vu, D. T.; Lira, C. T.; Miller, D. J. Reaction Kinetics for the Heterogeneously Catalyzed Esterification of Succinic Acid with Ethanol. Ind. Eng. Chem. Res. 2008, 47, 5313. (27) Steinigeweg, S.; Gmehling, J. n-Butyl Acetate Synthesis via Reactive Distillation: Thermodynamic Aspects, Reaction Kinetics, Pilot-Plant Experiments, and Simulation Studies. Ind. Eng. Chem. Res. 2002, 41, 5483. (28) Taylor, R.; Krishna, R. Modelling Reactive Distillation. Chem. Eng. Sci. 2000, 55, 5183. (29) Chiang, S. F.; Kuo, C. L.; Yu, C. C.; Wong, D. S. H. Design Alternatives for the Amyl Acetate Process: Coupled Reactor/Column and Reactive Distillation. Ind. Eng. Chem. Res. 2002, 41, 3233. (30) Tang, Y. T.; Chen, Y. W.; Huang, H. P.; Yu, C. C.; Hung, S. B.; Lee, M. J. Design of Reactive Distillations for Acetic Acid Esterification. AIChE J. 2005, 51, 1683. (31) Lin, Y. D.; Chen, J. H.; Cheng, J. K.; Huang, H. P.; Yu, C. C. Process Alternatives for Methyl Acetate Conversion Using Reactive Distillation. 1. Hydrolysis. Chem. Eng. Sci. 2008, 63, 1668. (32) Douglas, J. M. Conceptual Design of Chemical Process; McGrawHill: New York, 1988. (33) Elliott, T. R.; Luyben, W. L. Quantitative Assessment of Controllability during the Design of a Ternary System with Two Recycle Streams. Ind. Eng. Chem. Res. 1996, 35, 3470.
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work is supported by the National Key Technology R&D Program of China (No. 2011BAE05B03).
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ABBREVIATIONS PVA = polyvinyl alcohol PTA = purified terephthalic acid PH = pseudohomogeneous RD = reactive distillation FID = flame ionization detector SRS = sum of the residual squares TAC = total annual cost
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REFERENCES
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