A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

doi:10.1016/j.cjche.2023.03.005

Abstract

Abstract: In this paper, the highly efficient ZnAlLa layered double oxide (ZnAlLa-LDO) catalyst was evaluated and used in methyl carbamate (MC) alcoholysis synthesis of dimethyl carbonate. Under optimal conditions, the MC conversion was 33.5% and the dimethyl carbonate (DMC) selectivity was up to 92.4% at 443 K and in 9 h. The prepared catalysts were well characterized to investigate the effect on the catalytic performance and reaction catalysis mechanism. The experimental results show that the addition of La adjusted the structure and chemical properties of ZnAl composite oxide and that the synergistic effect among Zn, Al and La play a key role in adjusting the acid-base properties and stability of the catalyst, which definitely improved the DMC selectivity and catalytic stability. Based on the proposed reaction mechanism, two kinetic models of the catalytic reaction were established and modified: Langmuir-Hinshelwood and power-rate law kinetic model. The good agreement between kinetic models and experimental data showed that the power-rate law kinetic model based on the elementary reactions is a suitable model for providing a theoretical basis. The pre-exponential factor and activation energy of the main reaction are 5.77×10⁷ and 77.60 kJ·mol^-1, respectively.

Key words: Methanol, Urea alcoholysis, Dimethyl carbonate, Kinetic model

摘要： In this paper, the highly efficient ZnAlLa layered double oxide (ZnAlLa-LDO) catalyst was evaluated and used in methyl carbamate (MC) alcoholysis synthesis of dimethyl carbonate. Under optimal conditions, the MC conversion was 33.5% and the dimethyl carbonate (DMC) selectivity was up to 92.4% at 443 K and in 9 h. The prepared catalysts were well characterized to investigate the effect on the catalytic performance and reaction catalysis mechanism. The experimental results show that the addition of La adjusted the structure and chemical properties of ZnAl composite oxide and that the synergistic effect among Zn, Al and La play a key role in adjusting the acid-base properties and stability of the catalyst, which definitely improved the DMC selectivity and catalytic stability. Based on the proposed reaction mechanism, two kinetic models of the catalytic reaction were established and modified: Langmuir-Hinshelwood and power-rate law kinetic model. The good agreement between kinetic models and experimental data showed that the power-rate law kinetic model based on the elementary reactions is a suitable model for providing a theoretical basis. The pre-exponential factor and activation energy of the main reaction are 5.77×10⁷ and 77.60 kJ·mol^-1, respectively.

关键词: Methanol, Urea alcoholysis, Dimethyl carbonate, Kinetic model

Mingxue Yin, Bo Jia, Kuiyi You, Bo Jin, Yangqiang Huang, Xiao Luo, Zhiwu Liang. A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol[J]. Chinese Journal of Chemical Engineering, 2023, 61(9): 9-23.

References

[1] D. Delledonne, F. Rivetti, U.Romano, Developments in the production and application of dimethylcarbonate, Appl. Catal. A Gen. 221 (1–2) (2001) 241–251.
[2] S. Sen, S. Patil, D.S. Argyropoulos, Methylation of softwood kraft lignin with dimethyl carbonate, Green Chem. 17 (2) (2015) 1077–1087.
[3] F. Aricò, P.Tundo, Dimethyl carbonate as a modern green reagent and solvent, Russ. Chem. Rev. 79 (6) (2010) 479–489.
[4] M.H. Wang, H. Wang, N. Zhao, W. Wei, Y.H.Sun, Synthesis of dimethyl carbonate from urea and methanol over solid base catalysts, Catal. Commun. 7 (1) (2006) 6–10.
[5] R. Bernini, F. Crisante, M.C. Ginnasi, A convenient and safe O-methylation of flavonoids with dimethyl carbonate (DMC), Molecules 16 (2) (2011) 1418–1425.
[6] Q.H. Cai, L. Zhang, Y.K. Shan, M.Y. He, Promotion of ionic liquid to dimethyl carbonate synthesis from methanol and carbon dioxide, Chin. J. Chem. 22 (5) (2004) 422–424.
[7] M.A. Pacheco, C.L.Marshall, Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive, Energy Fuels 11 (1) (1997) 2–29.
[8] H.Y. Cui, T. Wang, F.J. Wang, C.R. Gu, P.L. Wang, Y.Y.Dai, Transesterification of ethylene carbonate with methanol in supercritical carbon dioxide, J. Supercrit. Fluids 30 (1) (2004) 63–69.
[9] T.W. Wu, I.L. Chien, CO₂ utilization feasibility study: dimethyl carbonate direct synthesis process with dehydration reactive distillation, Ind. Eng. Chem. Res. 59 (3) (2020) 1234–1248.
[10] Y. Ono., Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block, Appl. Catal. A Gen. 155 (2) (1997) 133–166.
[11] K. Shukla, V.C.Srivastava, Diethyl carbonate synthesis by ethanolysis of urea using Ce-Zn oxide catalysts, Fuel Process. Technol. 161 (2017) 116–124.
[12] X. Jin, P. Bobba, N. Reding, Z.W. Song, P.S. Thapa, G. Prasad, B. Subramaniam, R.V.Chaudhari, Kinetic modeling of carboxylation of propylene oxide to propylene carbonate using ion-exchange resin catalyst in a semi-batch slurry reactor, Chem. Eng. Sci. 168 (2017) 189–203.
[13] A.H. Tamboli, A.A. Chaugule, H.Kim, Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol, Chem. Eng. J. 323 (2017) 530–544.
[14] Y. Arikawa, T. Nakamura, S. Ogushi, K. Eguchi, K. Umakoshi, Fixation of atmospheric carbon dioxide by ruthenium complexes bearing an NHC-based pincer ligand: formation of a methylcarbonato complex and its methylation, Dalton Trans. 44 (12) (2015) 5303–5305.
[15] W.B. Zhao, F. Wang, W.C. Peng, N. Zhao, J.P. Li, F.K. Xiao, W. Wei, Y.H.Sun, Synthesis of dimethyl carbonate from methyl carbamate and methanol with zinc compounds as catalysts, Ind. Eng. Chem. Res. 47 (16) (2008) 5913–5917.
[16] L.L. Xu, Brief analysis of synthesis technology of dimethyl carbonate. Guangzhou Chemical Industry. 49(9)(2021)141-142.
[17] P.J. Liu, S.Y. Shao, X.J. Zhou, H.F. Qiu, Y.M. Liu, Study on development and application process of dimethyl carbonate. Coal and Chemical Industry. 45(5)(2022) 126-131.
[18] B.L. Yang, D.P. Wang, H.Y. Lin, J.J. Sun, X.P.Wang, Synthesis of dimethyl carbonate from urea and methanol catalyzed by the metallic compounds at atmospheric pressure, Catal. Commun. 7 (7) (2006) 472–477.
[19] M.H. Wang, H. Wang, N. Zhao, Wei, Y.H. Sun, High-yield synthesis of dimethyl carbonate from urea and methanol using a catalytic distillation process, Ind. Eng. Chem. Res. 46 (9) (2007) 2683–2687.
[20] H. Wang, B. Lu, X.G. Wang, J.W. Zhang, Q.H.Cai, Highly selective synthesis of dimethyl carbonate from urea and methanol catalyzed by ionic liquids, Fuel Process. Technol. 90 (10) (2009) 1198–1201.
[21] D.F. Wang, X.L. Zhang, Y.Y. Gao, F.K. Xiao, W. Wei, Y.H.Sun, Zn/Fe mixed oxide: heterogeneous catalyst for the synthesis of dimethyl carbonate from methyl carbamate and methanol, Catal. Commun. 11 (5) (2010) 430–433.
[22] D.F. Wang, X.L. Zhang, W.B. Zhao, W.C. Peng, N. Zhao, F.K. Xiao, W. Wei, Y.H. Sun, Synthesis of dimethyl carbonate from methyl carbamate and methanol catalyzed by mixed oxides from hydrotalcite-like compounds, J. Phys. Chem. Solids 71 (4) (2010) 427–430.
[23] D.F. Wang, X.L. Zhang, Y.Y. Gao, F.K. Xiao, W. Wei, Y.H.Sun, Synthesis of dimethyl carbonate from methyl carbamate and methanol over lanthanum compounds, Fuel Process. Technol. 91 (9) (2010) 1081–1086.
[24] B. Jia, X.Y. Sun, M. Chen, J. Jian, K.Y. You, H.A. Luo, Y.Q. Huang, X. Luo, B. Jin, N.L. Wang, Z.W. Liang, Selective preparation and reaction kinetics of dimethyl carbonate from alcoholysis of methyl carbamate with methanol over ZnAl-LDO, React. Chem. Eng. 6 (10) (2021) 1854–1868.
[25] J.I. Di Cosimo, V.K. Dıez, M. Xu, E. Iglesia, C.R. Apesteguıa, Structure and surface and catalytic properties of Mg-Al basic oxides, J. Catal. 178 (2) (1998) 499–510.
[26] Q. Wang, L.F. Chen, S.L. Guan, X. Zhang, B. Wang, X.Z. Cao, Z. Yu, Y.F. He, D.G. Evans, J.T. Feng, D.Q. Li, Ultrathin and vacancy-rich CoAl-layered double hydroxide/graphite oxide catalysts: promotional effect of cobalt vacancies and oxygen vacancies in alcohol oxidation, ACS Catal. 8 (4) (2018) 3104–3115.
[27] J. Zhang, T.T. Yan, Y.S. Yang, J.L. Sun, Y.J. Lin, M. Wei, Zn-Zr-Al oxides derived from hydrotalcite precursors for ethanol conversion to diethyl carbonate, Chin. J. Catal. 40 (4) (2019) 515–522.
[28] W.S. Yang, Y. Kim, P.K.T. Liu, M. Sahimi, T.T.Tsotsis, A study by in situ techniques of the thermal evolution of the structure of a Mg-Al-CO₃ layered double hydroxide, Chem. Eng. Sci. 57 (15) (2002) 2945–2953.
[29] E. Rodrigues, P. Pereira, T. Martins, F. Vargas, T. Scheller, J. Correa, J. Del Nero, S.G.C. Moreira, W. Ertel-Ingrisch, C.P. De Campos, A.Gigler, Novel rare earth (Ce and La) hydrotalcite like material: synthesis and characterization, Mater. Lett. 78 (2012) 195–198.
[30] W. Joe, H.J. Lee, U.G. Hong, Y. Ahn, C. Song, B. Kwon, I. Song, Synthesis of dimethyl carbonate from urea and methanol over ZnO(X)-CeO₂(1 - X) catalysts prepared by a Sol-gel method, J. Ind. Eng. Chem. 18 (3) (2012) 1018–1022.
[31] P. Kumar, V.C. Srivastava, I.M.Mishra, Synthesis and characterization of Ce-La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate, Catal. Commun. 60 (2015) 27–31.
[32] D.F. Wang, X.L. Zhang, J. Ma, H.W. Yu, J.Z. Shen, W.Wei, La-modified mesoporous Mg-Al mixed oxides: effective and stable base catalysts for the synthesis of dimethyl carbonate from methyl carbamate and methanol, Catal. Sci. Technol. 6 (5) (2016) 1530–1545.
[33] W. Joe, H.J. Lee, U.G. Hong, Y. Ahn, C. Song, B. Kwon, I. Song, Urea methanolysis to dimethyl carbonate over ZnO-CeO₂-MO (MO: La₂O₃, Y₂O₃, Co₂O₃, Ga₂O₃, and ZrO₂) catalysts, J. Ind. Eng. Chem. 18 (5) (2012) 1730–1735.
[34] J. Pérez-Ramırez, J. Overeijnder, F. Kapteijn, J.A.Moulijn, Structural promotion and stabilizing effect of Mg in the catalytic decomposition of nitrous oxide over calcined hydrotalcite-like compounds, Appl. Catal. B Environ. 23 (1) (1999) 59–72.
[35] D. Wang, X. Zhang, W. Wei, Y. Sun, Synthesis of dimethyl carbonate from methyl carbamate and methanol using a fixed-bed reactor, Chem. Eng. Technol. 35 (12) (2012) 2183–2188.
[36] X.M. Wu, M. Kang, N. Zhao, W. Wei, Y.H.Sun, Dimethyl carbonate synthesis over ZnO-CaO bi-functional catalysts, Catal. Commun. 46 (2014) 46–50.
[37] Dengfeng, Wang, Influence of Y on the performance of Mg-Al-Y catalysts via hydrotalcite-like precursors for the synthesis of diethyl carbonate from ethyl carbamate and ethanol, Fuel Process. Technol. 167 (2017) 404–415.
[38] Yubo, Ma, Environment-friendly synthesis of diethyl carbonate via ethyl carbamate alcoholysis over cerium oxide catalyst, J. Environ. Manag. 232 (2019) 952–956.
[39] Z. Liu, J.A. Cortés-Concepción, M. Mustian, M.D.Amiridis, Effect of basic properties of MgO on the heterogeneous synthesis of flavanone, Appl. Catal. A Gen. 302 (2) (2006) 232–236.
[40] G.D. Wu, X.L. Wang, B. Chen, J.P. Li, N. Zhao, W. Wei, Y.H.Sun, Fluorine-modified mesoporous Mg-Al mixed oxides: mild and stable base catalysts for O-methylation of phenol with dimethyl carbonate, Appl. Catal. A Gen. 329 (2007) 106–111.
[41] Peng, Liu, Promotional effect of transition metal doping on the basicity and activity of calcined hydrotalcite catalysts for glycerol carbonate synthesis, Appl. Catal. B Environ. 144 (2014) 135–143.
[42] M. Liu, M. Konstantinova, L. Negahdar, J.McGregor, The role of Zn in the sustainable one-pot synthesis of dimethyl carbonate from carbon dioxide, methanol and propylene oxide, Chem. Eng. Sci. 231 (2021) 116267.
[43] J.J. Sun, B.L. Yang, X.P. Wang, D.P. Wang, H.Y. Lin, Synthesis of dimethyl carbonate from urea and methanol using polyphosphoric acid as catalyst, J. Mol. Catal. A Chem. 239 (1–2) (2005) 82–86.
[44] X.M. Wu, M. Kang, Y.L. Yin, F. Wang, N. Zhao, F.K. Xiao, W. Wei, Y.H.Sun, Synthesis of dimethyl carbonate by urea alcoholysis over Zn/Al bi-functional catalysts, Appl. Catal. A Gen. 473 (2014) 13–20.