Zn-Ca-Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1, 2-propylene glycol

doi:10.1016/j.cjche.2016.11.003

Abstract

Abstract: A series of Zn-Ca-Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate (PC) from 1,2-propylene glycol (PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn-Ca-Al catalysts, according to the time dependences of reaction intermediates and products.

Key words: Propylene carbonate, 1,2-Propylene glycol, Urea, Catalysis, Alcoholysis

摘要： A series of Zn-Ca-Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate (PC) from 1,2-propylene glycol (PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn-Ca-Al catalysts, according to the time dependences of reaction intermediates and products.

关键词: Propylene carbonate, 1,2-Propylene glycol, Urea, Catalysis, Alcoholysis

Sen Liu, Suhong Sun, Xuehui Tian, Peiyong Sun, Shenghong Zhang, Zhilong Yao. Zn-Ca-Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1, 2-propylene glycol[J]. , 2017, 25(5): 609-616.

References

[1] Q. Li, N. Zhao, W. Wei, Y. Sun, Catalytic performance of metal oxides for the synthesis of propylene carbonate from urea and 1,2-propanediol, J. Mol. Catal. A Chem. 270(2007) 44-49.
[2] A.I. Adeleye, D. Patel, D. Niyogi, B. Saha, Efficient and greener synthesis of propylene carbonate from carbon dioxide and propylene oxide, Ind. Eng. Chem. Res. 53(2014) 18647-18657.
[3] D. Wu, Y. Guo, S. Geng, Y. Xia, Synthesis of propylene carbonate from urea and 1,2-propylene glycol in a monolithic stirrer reactor, Ind. Eng. Chem. Res. 52(2013) 1216-1223.
[4] J. Holtbruegge, M. Leimbrink, P. Lutze, A. Gorak, Synthesis of dimethyl carbonate and propylene glycol by transesterification of propylene carbonate with methanol:Catalyst screening, chemical equilibrium and reaction kinetics, Chem. Eng. Sci. 104(2013) 347-360.
[5] P. Kumar, V.C. Srivastava, I.M. Mishra, Dimethyl carbonate synthesis from propylene carbonate with methanol using Cu-Zn-Al catalyst, Energy Fuel 29(2015) 2664-2675.
[6] G. Zhang, H. An, X. Zhao, Y. Wang, Preparation of Ca-Zn-Al oxides and their catalytic performance in the one-pot synthesis of dimethyl carbonate from urea, 1,2-propylene glycol, and methanol, Ind. Eng. Chem. Res. 54(2015) 3515-3523.
[7] M. North, R. Pasquale, C. Young, Synthesis of cyclic carbonates from epoxides and CO₂, Green Chem. 12(2010) 1514-1539.
[8] S. Bagheri, N.M. Julkapli, W.A. Yehye, Catalytic conversion of biodiesel derived raw glycerol to value added products, Renew. Sust. Energ. Rev. 41(2015) 113-127.
[9] Q. Li, W. Peng, Q. Guo, J. Li, N. Zhao, F. Xiao, W. Wei, Y. Sun, Y. Yu, Q. Zhang, Synthesis of propylene carbonate from urea and propylene glycol using ZnO catalyst, J. Fuel Chem. Technol. 35(2007) 447-451.
[10] S. Wu, S. Liu, G. Wang, MgO used as catalyst for synthesis of propylene carbonate freom urea and 1,2-propylene glycol, Fine Chem. 25(2008) 388-391.
[11] T. Zhang, B. Zhang, L. Li, N. Zhao, F. Xiao, Zn-Mg mixed oxide as high-efficiency catalyst for the synthesis of propylene carbonate by urea alcoholysis, Catal. Commun. 66(2015) 38-41.
[12] H. An, Y. Ma, X. Zhao, Y. Wang, Preparation of Zn-Al oxide catalyst and its catalytic performance in propylene carbonate synthesis from urea and propylene glycol on a fixed-bed reactor, Catal. Today 264(2016) 136-143.
[13] Z. Du, L. Liu, H. Yuan, J. Xiong, B. Zhou, Y. Wu, Synthesis of propylene carbonate from alcoholysis of urea catalyzed by modified hydroxyapatites, Chin. J. Catal. 31(2010) 371-373.
[14] Z. Du, F. Chen, Z. Lin, X. Li, H. Yuan, Y. Wu, Effect of MgO on the catalytic performance of MgTiO₃ in urea alcoholysis to propylene carbonate, Chem. Eng. J. 278(2015) 79-84.
[15] Z. Gao, S. Wang, C. Xia, Synthesis of propylene carbonate from urea and 1,2-propanediol over a magnetic nanoparticle, J. Mol. Catal. (China) 23(2009) 304-307.
[16] Z. Du, Z. Lin, F. Chen, X. Hu, Y. Ding, R. Chi, Y. Wu, Synthesis of propylene carbonate from urea and 1,2-propylene glycol over MnO₂/γ-Al₂O₃ catalyst modified by NaOH, CIESC J. 65(2014) 4333-4339(in Chinese).
[17] Q. Li, N. Zhao, W. Wei, Y. Sun, Synthesis of propylene carbonate from urea and propylene glycol, Stud. Surf. Sci. Catal. 153(2004) 573-576.
[18] X. Zhao, Z. Jia, Y. Wang, Clean synthesis of propylene carbonate from urea and 1,2-propylene glycol over zinc-iron double oxide catalyst, J. Chem. Technol. Biotechnol. 81(2006) 794-798.
[19] G. Yu, X. Chen, C. Chen, Synthesis of propylene carbonate from urea and 1,2-propylene glycol over ZnO/NaY catalyst, React. Kinet. Catal. Lett. 97(2009) 69-75.
[20] Z. Gao, S. Wang, C. Xia, Synthesis of propylene carbonate from urea and 1,2-propanediol, Chin. Chem. Lett. 20(2009) 131-135.
[21] X. Zhang, D. Wang, C. Liu, L. Shi, Q. Fang, Z. Song, Synthesis of propylene carbonate from urea and 1,2-propylene glycol over lanthanum compound catalysts, Petrochem. Technol. 44(2015) 1182-1187.
[22] D. Bai, X. Zhang, J. Wu, H. Li, Y. Wang, D. Wang, Synthesis of propylene carbonate from ureaand 1,2-propyleneglycol over zinc salts, Chem. Eng. 43(2015) 63-67(in Chinese).
[23] X. Zhao, Y. Zhang, Y. Wang, Synthesis of propylene carbonate from urea and 1,2-propylene glycol over a zinc acetate catalyst, Ind. Eng. Chem. Res. 43(2004) 4038-4042.
[24] G. Zhang, Y. Geng, H. An, X. Zhao, Y. Wang, Synthesis of propylene carbonate from CO₂ and 1,2-propylene glycol on fixed-bed reactor and its reaction mechanism catalyzed by Zn(OAc)₂/AC, CIESC J. 66(2015) 567-875(in Chinese).
[25] Q. Li, W. Zhang, N. Zhao, W. Wei, Y. Sun, Synthesis of cyclic carbonates from urea and diols over metal oxides, Catal. Today 115(2006) 111-116.
[26] T. Shu, W. Mo, H. Xiong, G. Li, Synthesis of propylene carbonate from urea and 1,2-propanediol catalyzed by hdrotalcite-like compounds, Petrochem. Technol. 35(2006) 11-14(in Chinese).
[27] D. Fakhrnasova, R.J. Chimentao, F. Medina, A. Urakawa, Rational and statistical approaches in enhancing the yield of ethylene carbonate in urea transesterification with ethylene glycol over metal oxides, ACS Catal. 5(2015) 6284-6295.
[28] J. Yu, Q. Ge, W. Fang, H. Xu, Influences of calcination temperature on the efficiency of CaO promotion over CaO modified Pt/γ-Al₂O₃ catalyst, Appl. Catal. A Chem. 395(2011) 114-119.
[29] C.K.S. Choong, L. Huang, Z. Zhong, J. Lin, L. Hong, L. Chen, Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al₂O₃:Ⅱ. Acidity/basicity, water adsorption and catalytic activity, Appl. Catal. A Chem. 407(2011) 155-162.
[30] Z. Liu, W. Zhao, F. Xiao, W. Wei, Y. Sun, One-pot synthesis of propylene glycol and dipropylene glycol over strong basic catalyst, Catal. Commun. 11(2010) 675-678.
[31] Y. Zhao, T. Chen, Y. Lei, G. Wang, J. Yao, Y. Wang, Synthesis of propylene carbonate from urea and 1,2-propylene glycol catalyzed by lead and zinc compounds, Fine Chem. 22(2005) 638-640(in Chinese).
[32] J. Zhou, D. Wu, B. Zhang, Y. Guo, Synthesis of propylene carbonate from urea and 1,2-propylene glycol over metal carbonates, Chem. Ind. Chem. Eng. Q. 17(2011) 323-331.
[33] A.M. Bernhard, D. Peitz, M. Elsener, A. Wokaun, O. Kröcher, Hydrolysis and thermolysis of urea and its decomposition byproducts biuret, cyanuric acid and melamine over anatase TiO₂, Appl. Catal. B Environ. 115(2012) 129-137.