Effects of Lithium Content on the Structural Properties and Catalytic Activities of CuLi/AC Catalysts in the Oxidative Carbonylation of Methanol to Dimethyl Carbonate

doi:10.7503/cjcu20130429

Abstract

Abstract:

The CuLi/AC(active carbon) catalysts with different lithium contents were prepared by microwave heating and tested in the oxidative carbonylation of methanol to dimethyl carbonate(DMC). The bulk and surface properties of the catalysts were characterized by means of X-ray diffraction(XRD), H₂-temperature program reduction(H₂-TPR), X-ray photoelectron spectrum(XPS), scanning electron microscope(SEM), and CO-temperature programe desorption(CO-TPD) techniques. The results show that the addition of moderate content of lithium into the Cu/AC catalyst enhances the auto-reduction of copper species to Cu⁰, leading to more well-dispersed Cu nanoparticles with more uniform grain size on the surface of active carbon. The cataly-tic performance is related to the concentration of Cu⁰ in the surface of CuLi/AC catalysts, indicating that Cu⁰species is the main active centers for the synthesis of DMC. The addition of lithium enhances CO weak adsorption centers, which favors the insertion reaction between CO molecules and Cu-OCH₃ intermediates, and thus effectively improve the catalytic activity of CuLi/AC catalysts. The STY(space time yield) of DMC firstly increases and then decreases with the content of lithium, and reaches the maximum of 540.6 mg·g^-1·h^-1 when the mass fraction of lithium is up to 0.15% in the catalysts, and the corresponding MeOH conversion and DMC selectivity are 4.5% and 81.4%, respectively.

Key words: CuLi/AC catalyst, Lithium promoter, Microwave irradiation, Dimethyl carbonate, Oxycarbonylation

CLC Number:

O643.3

TrendMD:

REN Jun, WANG Dong-Lei, PEI Yong-Li, QIN Zhi-Feng, LIN Jian-Ying, LI Zhong. Effects of Lithium Content on the Structural Properties and Catalytic Activities of CuLi/AC Catalysts in the Oxidative Carbonylation of Methanol to Dimethyl Carbonate[J]. Chem. J. Chinese Universities, 2013, 34(11): 2594.

References

[1] Buysch H. J., Krimm H., Boehm S., Process for the Preparation of Dimethyl Carbonate, US4335051, 1982-06-15

[2] Delledonne D., Rivetti F., Romano U., Applied Catalysis A: General, 2001, 221(1/2), 241-251

[3] Song Y. B., Luo A. G., Du Y. H., Fang Y. W., Progress in Chemistry, 2008, 20(2/3), 221-226(宋一兵, 罗爱国, 杜玉海, 方奕文. 化学进展, 2008, 20(2/3), 221-226)

[4] Pacheco M. A., Marshall C. L., Energy and Fuels, 1997, 11(1), 2-29

[5] Tomishige K., Sakaihori T., Sakai S. I., Fujimoto K., Applied Catalysis A: General, 1999, 181(1), 95-102

[6] Wang Y. J., Zhao X. Q., Yuan B. G., Zhang B. C., Cong J. S., Journal of Fuel Chemistry and Technology, 1997, 25(4), 323-327(王延吉, 赵新强, 苑保国, 张秉常, 丛津生. 燃料化学学报, 1997, 25(4), 323-327)

[7] Jiang R. X., Wang Y. J., Zhao X. Q., Wang S. F., Jin C. Q., Zhang C. F., Journal of Molecular Catalysis A: Chemical, 2002, 185(1/2), 159-166

[8] Jiang R. X., Wang Y. J., Zhao X. Q., Wang S. F., Journal of Fuel Chemistry and Technology, 2000, 28(5), 478-480(姜瑞霞, 王延吉, 赵新强, 王淑芳. 燃料化学学报, 2000, 28(5), 478-480)

[9] King S. T., Journal of Catalysis, 1996, 161, 530-538

[10] King S. T., Catalysis Today, 1997, 33, 173-182

[11] Drake I. J., Fujdala K. L., Bell A. T., Tilley T. D., Journal of Catalysis, 2005, 230(1), 14-27

[12] Richter M., Fait M. J. G., Eckelt R., Schneider M., Radnik J., Heidemann D., Fricke R., Journal of Catalysis, 2007, 245, 11-24

[13] Wang R. Y., Li Z., Zheng H. Y., Xie K. C., Chinese Journal of Catalysis, 2010, 31(7), 851-856(王瑞玉, 李忠, 郑华艳, 谢克昌. 催化学报, 2010, 31(7), 851-856)

[14] Li Z., Wen C. M., Wang R. Y., Zheng H. Y., Xie K. C., Chem. J. Chinese Universities, 2009, 30(10), 2024-2031(李忠, 文春梅, 王瑞玉, 郑华艳, 谢克昌. 高等学校化学学报, 2009, 30(10), 2024-2031)

[15] Li Z., Wen C. M., Zheng H. Y., Xie K. C., Chem. J. Chinese Universities, 2010, 31(1), 145-152(李忠, 文春梅, 郑华艳, 谢克昌. 高等学校化学学报, 2010, 31(1), 145-152)

[16] Li Z., Zhu Q. F., Wang R. Y., Niu Y. Y., Zheng H. Y., Chinese J. Inorg. Chem., 2011, 27(4), 718-724(李忠, 朱琼芳, 王瑞玉, 牛燕燕, 郑华艳. 无机化学学报, 2011, 27(4), 718-724)

[17] Zhang R. G., Zheng H. Y., Wang B. J., Li Z., Chem. J. Chinese Universities, 2010, 31(6), 1246-1251(章日光, 郑华艳, 王宝俊, 李忠. 高等学校化学学报, 2010, 31(6), 1246-1251)

[18] Zhang R. G., Song L. Z., Wang B. J., Li Z., Journal of Computational Chemistry, 2012, 33, 1101-1110

[19] Egbebi A., Schwartz V., Overbury S. H., Spivey J. J., Catalysis Today, 2010, 149, 91-97

[20] Schwartz V., Campos A., Egbebi A., Spivey J. J., Overbury S. H., American Chemical Society Catalysis, 2011, 1, 1298-1306

[21] Ren J., Liu S. S., Li Z., Lu X. L., Xie K. C., Applied Catalysis A: General, 2009, 366, 93-101

[22] Jiang S. H., Ren J., Industrial Catalysis, 2010, 18(2), 21-24(姜少华, 任军. 工业催化, 2010, 18(2), 21-24)

[23] Li Z., Liu S. S., Ren J., Niu Y. Y., Zheng H. Y., Zhao Q., Cui L. P., Chinese Journal of Catalysis, 2010, 31, 683-688(李忠, 刘树森, 任军, 牛燕燕, 郑华艳, 赵强, 崔丽萍. 催化学报, 2010, 31, 683-688)

[24] Wang S. R., Yin Q. Q., Li X. B., Chem. Res. Chinese Universities, 2012, 28(1), 119-123

[25] Li Z., Fu T. J., Wang R. Y., Niu Y. Y., Zheng H. Y., Chem. J. Chinese Universities, 2011, 32(6), 1366-1372(李忠, 付廷俊, 王瑞玉, 牛燕燕, 郑华艳. 高等学校化学学报, 2011, 32(6), 1366-1372)

[26] Han M. S., Lee B. G., Ahn B. S., Moon D. J., Hong S. I., Journal of Molecular Catalysis A: Chemical, 2003, 203, 137-143

[27] Zang Y. H., Briggs D. N., Smit E. D., Bell A. T., Journal of Catalysis, 2007, 251, 443-452