Coupled Reaction/Distillation Process for Hydrolysis of Methyl Acetate

Abstract

Abstract: A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The results show that at the molar ratio of water to methyl acetate about 4.0-5.0 in the feed stream and the volume ratio of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5% (by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process we proposed before, this process can cut down 47.6% energy consumption and a distillation column.

Key words: methyl acetate, hydrolysis, simulation

摘要： A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The results show that at the molar ratio of water to methyl acetate about 4.0-5.0 in the feed stream and the volume ratio of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5% (by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process we proposed before, this process can cut down 47.6% energy consumption and a distillation column.

关键词: methyl acetate, hydrolysis, simulation

ZHAO Suying, HUANG Jingzhao, WANG Liang'en, HUANG Guoqiang. Coupled Reaction/Distillation Process for Hydrolysis of Methyl Acetate[J]. , 2010, 18(5): 755-760.

赵素英, 黄镜钊, 王良恩, 黄国强. Coupled Reaction/Distillation Process for Hydrolysis of Methyl Acetate[J]. , 2010, 18(5): 755-760.

References

1 Ma, Y.G., Mou, C.G., Wu, S.H., Technology of PVA Production, Textile Industry Press, Beijing (1986). (in Chinese)
2 Wang, C.X., “Study on hydrolysis of methyl acetate in a catalytic distillation column”, Chin. J. Chem. Eng., 9, 382-387 (2001).
3 Pan, Y.B., Li, W.X., Shen, P.D., Wan, H., Han, M.J., Guan, G.F., “Study on hydrolysis of methyl acetate from production of purified terephthalic acid by catalytic distillation”, Chem. Reac. Eng. & Tech., 25, 132-136 (2009). (in Chinese)
4 Wang, J.F., Ge, X.D., Wang, Z.W, Jin, Y., “Experimental studies on the catalytic distillation for hydrolysis of methyl acetate”, Chem. Eng. Technol., 24, 155-159 (2001).
5 Sander, S., Flisch, C., “Methyl acetate hydrolysis in a reactive divided wall column”, Chem. Eng. Res. Des., 85,149-154 (2007).
6 Yuan, P.Q., Chen, Z.M., Liu, T., Yuan, W.K., “Hydrolysis of methyl acetate under near or supercritical condition”, Chem. J. Chinese U., 24, 1241-1245 (2003). (in Chinese)
7 Fuchigami, Y., “Hydrolysis of methyl acetate in distillation column packed with reactive packing of ion exchange resin”, J. Chem. Eng. Jpn., 23, 354-359 (1990).
8 Xiao, J., Liu, J.Q., Li, J.T., Jiang, X.H., Zhang, Z.B., “Increase MeOAc conversion in PVA production by replacing the fixed bed reactor with a catalytic distillation column”, Chem. Eng. Sci., 56, 6553-6562 (2001). 9
Wang, L.E., Su, W.R., Zhao, Z.S., Liu, J.Q., Wu, Y.X., Shen, J.N., Qiu, T., “Industrial application of the catalytic distillation technique in hydrolysis of methyl acetate”, Viny. Commu., 21, 10-12 (2001). (in Chinese)
10 Wu, Y.X., Wang, L.E., Zhao, Z.S., Tan, T.E., “Mass transfer model for catalyst capsule in catalyst distillation (I) mathematical model”, CIESC J., 53, 503-507 (2002). (in Chinese)
11 Wu, Y.X., Wang, L.E., Zhao, Z.S., Tan, T.E., “Mass transfer model for catalyst capsule in catalyst distillation (II) measurement and calculation of effectiveness factor”, CIESC J., 53, 508-512 (2002). (in Chinese)
12 Kim, K., Roh, H.D., “Reactive distillation process and equipment for the production of acetic acid and methanol from methyl acetate hydrolysis”, U.S. Pat., .5970770 (1998).
13 Moritz, P., Hasse, H., “Fluid dynamics in reactive distillation packing Katapak S”, Chem. Eng. Sci., 54, 1367-13741 (1999).
14 Dirk-Faitakis, C.B., An, W.Z., Lin, T.B., Chuang, K.T., “Catalytic distillation for simultaneous hydrolysis of methyl acetate and etherification of methanol”, Chem. Eng. Process., 48, 1080-1087 (2009).
15 Gmehling, J., B lts, R., “Azeotropic data for binary and ternary systems at moderate pressures”, J. Chem. Eng. Data., 41, 202-209 (1996).
16 Bessling, B., L ning, J.M., Ohligschl ger, A., Schembecker, G., Sundmacher, K., “Investigations on the synthesis of methyl acetate in a heterogeneous reactive distillation process”, Chem. Eng. Technol., 21, 393-400 (1998).
17 Wu, Y.X., Zhao, Z.S., Wang, L.E., Zhao, S.Y., “Kinetics of hydrolysis of methyl acetate and the effectiveness factor of catalyst capsule”, Eng. Chem. Meta., 20, 241-246 (1999). (in Chinese)
18 Wang, L.E., Liu, J.Q., Su, W.R., Zhao, Z.S., Zheng, W.H., Zhang, J.L., “Catalytic distillation process for methyl acetate hydrolysis and its equipments”, China Pat., 97101306.3 (1997).
19 Wang, L.E., Zhao, Z.S., Qiu, T., Zhao, S.Y., Zheng, H.D., Qiu, T.R., Su, W.R., Xie, Y.H., Luo, D.H., “Byproduct methyl acetate hydrolysis process and its equipments in the industry of PTA”, China Pat., 200610124556.7 (2006).
20 Wu, Y.X., Tan, T.E., Wang, L.E., Zhao. Z.S., “Simulation of the catalytic distillation process for hydrolysis of methyl acetate”, Eng. Chem. Meta., 21, 24-29 (2000). (in Chinese)
21 P pken, T., G tze, 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., 39, 2601-2611 (2000).

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