Process optimization study on the carbonylation of methyl acetate

doi:10.1016/j.cjche.2018.01.024

Abstract

Abstract: Acetic anhydride is the important organic chemical raw material, and is used widely in chemical industry, pharmaceutical industry, dyes, spices and other fields. In this paper, the process of carbonylation of methyl acetate in rhodium iodine catalyst system was studied, and the suitable reaction conditions were determined. At the same time, the kinetic model was established. The optimum reaction conditions were as follows:the reaction pressure was 5 MPa, the hydrogen content was 8%, the amount of iodomethane was 15%, the amount of lithium iodide was 3%, the reaction temperature was 150℃ and the reaction time is 3 h. Under the above reaction conditions, the selectivity of the reaction is close to 100% and the conversion is as high as 92%. The macroscopic kinetic model of the reaction was established in the temperature range of 120℃-150℃. The reaction is an irreversible reaction without the formation of by-products and the dynamic equation is also given in the Conclusions section.

Key words: Carbonylation, Rhodium iodine catalyst, Reaction conditions, Kinetics

摘要： Acetic anhydride is the important organic chemical raw material, and is used widely in chemical industry, pharmaceutical industry, dyes, spices and other fields. In this paper, the process of carbonylation of methyl acetate in rhodium iodine catalyst system was studied, and the suitable reaction conditions were determined. At the same time, the kinetic model was established. The optimum reaction conditions were as follows:the reaction pressure was 5 MPa, the hydrogen content was 8%, the amount of iodomethane was 15%, the amount of lithium iodide was 3%, the reaction temperature was 150℃ and the reaction time is 3 h. Under the above reaction conditions, the selectivity of the reaction is close to 100% and the conversion is as high as 92%. The macroscopic kinetic model of the reaction was established in the temperature range of 120℃-150℃. The reaction is an irreversible reaction without the formation of by-products and the dynamic equation is also given in the Conclusions section.

关键词: Carbonylation, Rhodium iodine catalyst, Reaction conditions, Kinetics

Baohe Wang, Baomin Ge, Jing Zhu, Lina Wang. Process optimization study on the carbonylation of methyl acetate[J]. Chin.J.Chem.Eng., 2018, 26(9): 1937-1942.

Baohe Wang, Baomin Ge, Jing Zhu, Lina Wang. Process optimization study on the carbonylation of methyl acetate[J]. Chinese Journal of Chemical Engineering, 2018, 26(9): 1937-1942.

References

[1] P.P. Sarmah, D.K. Dutta, Rhodium (I) carbonyl complexes of quinoline carboxylic acid:Synthesis, reactivity and catalytic carbonylation reaction, J. Mol. Catal. A Chem. 372(2013) 1-5.

[2] Y. Liu, G. Ding, Q. Zhao, The preparation technology and application for acetic anhydride at home and abroad, Tianjin Chem. Ind. 2(2005) 5.

[3] R.S. Drago, E.D. Nyberg, Ionic attachment as a feasible approach to heterogenizing anionic solution catalysts carbonylation of methanol, Inorg. Chem. 20(1981) 641-644.

[4] D. Forster, Mechanistic pathways in the catalytic carbonylation of methanol by rhodium and iridium complexes, Adv. Organomet. Chem. 17(1979)255-267.

[5] F.E. Paulik, J.F. Roth, Novel catalysts for the low-pressure carbonylation of methanol to acetic acid, Chem. Commun. (24) (1968) 1578a.

[6] P.M. Maitlis, A. Haynes, G.J. Sunley, M.J. Howard, Methanol carbonylation revisited:thirty years on, J. Chem. Soc. Dalton Trans. (11) (1996)2187-2196.

[7] G.J. Sunley, J.W. Derrick, High productivity methanol carbonylation catalysis using iridium:The Cativa^TM process for the manufacture of acetic acid, Catal. Today 58(2000)293-307.

[8] B. L. Smith, G. P. Torrence, A. Aguilo, J. S. Alder, Methanol carbonylation process:U. S. Pat., 5144068, Sep 1, 1992.

[9] C.M. Thomas, G. Süss-Fink, Ligand effects in the rhodium-catalyzed carbonylation of methanol, Coordin. Chem. Rev. 243(2003) 125-142.

[10] G. Zhang, Z. Li, H. Zheng, T. Fu, Y. Ju, Y. Wang, Influence of the surface oxygenated groups of activated carbon on preparation of a nano Cu/AC catalyst and heterogeneous catalysis in the oxidative carbonylation of methanol, Appl. Catal. B Environ. 179(2015) 95-105.

[11] Y. Chen, D. Liu, Reductive carbonylation of methanol for ethanol production in Rh-Ru-dppp-methyl iodide catalytic system under mild conditions-The effect of lithium salts and catalyst composition, Fuel Process. Technol. 171(2018) 301-307.

[12] J.S. Nam, A.R. Kim, D.M. Kim, T.S. Chang, B.S. Kim, J.W. Bae, Novel heterogeneous Rh-incorporated graphitic-carbon nitride for liquid-phase carbonylation of methanol to acetic acid, Catal. Commun. 99(2017) 141-145.

[13] P.K. Saikia, P.P. Sarmah, B.J. Borah, L. Saikia, D.K. Dutta, Functionalized montmorillonite supported rhodium complexes:Efficient catalysts for carbonylation of methanol, J. Mol. Catal. A Chem. 412(2016)27-33.

[14] J. Cook, Preparation of anhydrides:U.S. Pat., 4534912, 1985.

[15] R. E. Allan, D. J. Watson, Process for the co-production of acetic anhydride and acetic acid:U.S. Pat., 6541666, 2003.

[16] T. H. Larkins, S. W. Polichnowski, G. C. Tustin, D. A. Young, Preparation of acetic anhydride:U.S. Pat., 4374070, 1983.

[17] W. C. Jones, E. H. Cwirko, Process for the manufacture of acetic anhydride:U.S. Pat., 5922911, 1999.

[18] D. Z. Jiang, X. B. Li, E. L. Wang, Multi dentate heterodesmic Rh catalyst and its prepn. Method. C.N. Pat., 1120468A, 1996.

[19] G. Q. Yuan, Z. Y. Liu, P. L. Pan, Catalyst System for Preparing Acetate and Acetic Anhydride by Carbonylation and Its Preparing Process. CN, 1997.

[20] S.W. Polichnowski, Transition-metal-catalyzed carbonylation of methyl acetate, J. Chem. Educ. 63(1986)206.

[21] C.M. Conifer, D.J. Law, G.J. Sunley, A.J. White, G.J. Britovsek, Lewis acids and Lewis acid-functionalized ligands in rhodium-catalyzed methyl acetate carbonylation, Organomet. Chem. 30(2011) 4060-4066.

[22] C.M. Conifer, D.J. Law, G.J. Sunley, A. Haynes, J.R. Wells, A.J. White, G.J. Britovsek, Dicarbonylrhodium (I) complexes of bipyridine ligands with proximate H-bonding substituents and their application in methyl acetate carbonylation, Eur. J. Inorg. Chem. (23) (2011) 3511-3522.

[23] M.J. Howard, M.D. Jones, M.S. Roberts, S.A. Taylor, C1 to acetyls:catalysis and process, Catal. Today 18(1993) 325-354.

[24] J.R. Zoeller, Eastman Chemical Company's "Chemicals from Coal" program:The first quarter century, Catal. Today 140(2009) 118-126.

[25] G. Luft, M.J. Schrod, Investigations of the synthesis of acetic anhydride by homogeneous catalysis:I. Catalytic system and process parameters, J. Mol. Catal. 20(1983) 175-184.

[26] T.W. Dekleva, D. Forster, Mechanistic aspects of transition-metal-catalyzed alcohol carbonylations, Adv. Catal. 34(1986) 81-130.