热扩散法制备MoO3/SiO2催化草酸二甲酯和苯酚酯交换反应

doi:10.1016/S1872-2067(14)60042-5

催化学报 ›› 2014, Vol. 35 ›› Issue (7): 1043-1053.DOI: 10.1016/S1872-2067(14)60042-5

热扩散法制备MoO₃/SiO₂催化草酸二甲酯和苯酚酯交换反应

张付宝^a,c, 余晓鹏^b, 马飞^a,d, 杨先贵^a,d, 胡静^a,d, 邓志勇^a,d, 王公应^a,d

a. 中国科学院成都有机化学研究所, 四川成都610041;
b. 四川理工学院材料与化学工程学院, 四川自贡643000;
c. 中国科学院大学, 北京100049;
d. 中国科学院成都有机化学有限公司, 四川成都610041

收稿日期:2013-12-07 修回日期:2014-01-20 出版日期:2014-06-28 发布日期:2014-06-28
通讯作者: 邓志勇,王公应
基金资助:
国家科技支撑计划（2013BAC11B05）；四川省青年科技创新团队专项计划（2013TD0010）.

Transesterification of dimethyl oxalate with phenol over a MoO₃/SiO₂ catalyst prepared by thermal spreading

Fubao Zhang^a,c, Xiaopeng Yu^b, Fei Ma^a,d, Xiangui Yang^a,d, Jing Hu^a,d, Zhiyong Deng^a,d, Gongying Wang^a,d

a. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China;
b. Department of Material and Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000, Sichuan, China;
c. University of Chinese Academy of Sciences, Beijing 100049, China;
d. Chengdu Organic Chemicals Co., Ltd., Chengdu 610041, Sichuan, China

Received:2013-12-07 Revised:2014-01-20 Online:2014-06-28 Published:2014-06-28
Supported by:
This work was supported by the National Key Technology R&D Program (2013BAC11B05) and the Special Project for the Outstanding Youth Innovation Team of Sichuan Province (2013TD0010).

摘要/Abstract

摘要：

采用热扩散法（TS）和等体积浸渍法制备了MoO₃/SiO₂催化剂用于草酸二甲酯和苯酚酯交换反应.结果表明，热扩散法制备的10%MoO₃/SiO₂-TS催化剂较等体积浸渍法制备的10%MoO₃/SiO₂-C催化剂具有更好的催化性能.运用X射线衍射、Raman光谱、X射线光电子能谱分析、吡啶吸附红外光谱、NH₃程序升温脱附等手段对催化剂进行了表征，发现虽然两种方法制备的催化剂都只有弱Lewis酸中心，钼均以氧化钼单体形式存在，未形成解离和聚合，但是10%MoO₃/SiO₂-TS催化剂较10%MoO₃/SiO₂-C催化剂表面钼含量更高且MoO₃分散得更好.在苯酚用量为0.2mol，10%MoO₃/SiO₂-TS催化剂用量为1.2g，反应温度为180℃，草酸二甲酯与苯酚的摩尔比为2，反应时间为4h的优化条件下，苯酚转化率可达70.9%，甲基苯基草酸酯和草酸二苯酯的收率分别达63.1%和7.7%.

关键词: 热扩散法, MoO₃/SiO₂催化剂, 甲基苯基草酸酯, 草酸二苯酯, 酯交换

Abstract:

MoO₃/SiO₂ catalysts for the transesterification of dimethyl oxalate (DMO) with phenol were prepared by both the thermal spreading (TS) and incipient wetness impregnation methods. The results showed that the 10%MoO₃/SiO₂ catalyst prepared by TS (10%MoO₃/SiO₂-TS) exhibited higher catalytic performance compared with the 10%MoO₃/SiO₂ catalyst prepared by incipient wetness impregnation (10%MoO₃/SiO₂-C). The catalysts were characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, pyridine-IR spectroscopy, and NH₃ temperature-programmed desorption. These analyses indicated that weak Lewis acid sites were formed on the catalyst surfaces and that the Mo species were present as monomeric MoO₃ rather than as isolated molybdenum oxide or polymolybdate species on both catalysts, although the 10%MoO₃/SiO₂-TS exhibited better dispersion of MoO₃ and a higher surface Mo content than the 10%MoO₃/SiO₂-C. Under the optimal transesterification reaction conditions (1.2 g 10%MoO₃/SiO₂-TS, T=180℃, n(DMO)/n(phenol)=2, t=4 h), the conversion of phenol was 70.9%, and the yields of methyl phenyl oxalate and diphenyl oxalate were 63.1% and 7.7%, respectively.

Key words: Thermal spreading method, MoO₃/SiO₂ catalyst, Methyl phenyl oxalate, Diphenyl oxalate, Transesterification

张付宝, 余晓鹏, 马飞, 杨先贵, 胡静, 邓志勇, 王公应. 热扩散法制备MoO₃/SiO₂催化草酸二甲酯和苯酚酯交换反应[J]. 催化学报, 2014, 35(7): 1043-1053.

Fubao Zhang, Xiaopeng Yu, Fei Ma, Xiangui Yang, Jing Hu, Zhiyong Deng, Gongying Wang. Transesterification of dimethyl oxalate with phenol over a MoO₃/SiO₂ catalyst prepared by thermal spreading[J]. Chinese Journal of Catalysis, 2014, 35(7): 1043-1053.

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参考文献

[1] Xu K X. Handbook of Fine Organic Chemical Raw Materials and Intermediates. Beijing: Chem Ind Press (徐克勋. 精细有机化工原料及中间体手册. 北京: 化学工业出版社), 1998
[2] Mei F M, Li G X, Mo W L. Modern Chem Ind (梅付名, 李光兴, 莫婉玲. 现代化工), 1999, 19: 13
[3] Andraos J. Pure Appl Chem, 2012, 84: 827
[4] Gong J L, Ma X B, Wang S P. Appl Catal A, 2007, 316: 1
[5] Wang G Y, Liu S Y, Chen T, Yin X. Fine Chem (王公应, 刘绍英, 陈彤, 殷霞. 精细化工), 2013, 30: 420
[6] Kanega R, Hayashi T, Yamanaka I. ACS Catal, 2013, 3: 389
[7] Murayama T, Hayashi T, Kanega R, Yamanaka I. J Phys Chem C, 2012, 116: 10607
[8] Fan G Z, Wang Z G, Zou B, Wang M. Fuel Process Technol, 2011, 92: 1052
[9] Li B J, Tang R Z, Chen T, Wang G Y. Chin J Catal (李碧静, 唐荣芝, 陈彤, 王公应. 催化学报), 2012, 33: 601
[10] Cao P, Yang X G, Tang C M, Yang J, Yao J, Wang Y, Wang G Y. Chin J Catal (曹平, 杨先贵, 唐聪明, 杨建, 姚洁, 王越, 王公应. 催化学报), 2009, 30: 853
[11] Katsumasa H, Ryoji S, Kashiwagi K, Yoichi I, Takashi D, Nishihira K, Tanaka S, Hirofumi I. US Patent 5892089. 1998
[12] Nishihira K, Tanaka S, Nishida Y, Hirofumi I, Fujitsu S, Katsumasa H, Ryoji S, Kashiwagi K, Takashi D. US Patent 5811573. 1998
[13] Liu Y, Ma X B, Wang S P, Gong J L. Appl Catal B, 2007, 77: 125
[14] Ma X B, Guo H L, Wang S P, Sun Y L. Fuel Process Technol, 2003, 83: 275
[15] Ma X B, Gong J L, Wang S P, He F, Guo H L, Yang X, Xu G H. J Mol Catal A, 2005, 237: 1
[16] Shi Y, Wang S P, Ma X B. Chem Eng J, 2011, 166: 744
[17] Wang S P, Shi Y, Ma X B. Microporous Mesoporous Mater, 2012, 156: 22
[18] Liu Y, Zhao G M, Liu G, Wu S J, Chen G H, Zhang W X, Sun H Y, Jia M J. Catal Commun, 2008, 9: 2022
[19] Liu G, Liu Y, Yang G, Li S Y, Zu Y H, Zhang W X, Jia M J. J Phys Chem C, 2009, 113: 9345
[20] Ma X B, Wang S P, Gong J L, Yang X, Xu G H. J Mol Catal A, 2004, 222: 183
[21] Wang S P, Ma X B, Guo H L, Gong J L, Yang X, Xu G H. J Mol Catal A, 2004, 214: 273
[22] Ma X B, Gong J L, Wang S P, Gao N, Wang D L, Yang X, He F. Catal Commun, 2004, 5: 101
[23] Ma X B, Gong J L, Yang X, Wang S P. Appl Catal A, 2005, 280: 215
[24] Liu Y, Wang S P, Ma X B. Ind Eng Chem Res, 2007, 46: 1045
[25] Ma X B, Gong J L, Wang S P, He F, Yang X, Wang G, Xu G H. J Mol Catal A, 2004, 218: 253
[26] Gong J L, Ma X B, Wang S P, Liu M Y, Yang X, Xu G H. J Mol Catal A, 2004, 207: 215
[27] Gong J L, Ma X B, Yang X, Wang S P, Wen S D. React Kinet Catal Lett, 2005, 84: 79
[28] Gong J L, Ma X B, Yang X, Wang S P, Gao N, Wang D L. Catal Lett, 2005, 99: 187
[29] Kotbagi T, Nguyen D L, Lancelot C, Lamonier C, Thavornprasert K A, Zhu W L, Capron M, Jalowiecki-Duhamel L, Umbarkar S, Dongare M, Dumeignil F. ChemSusChem, 2012, 5: 1467
[30] Biradar A V, Umbarkar S B, Dongare M K. Appl Catal A, 2005, 285: 190
[31] Chen C X, Peng J S, Li B, Hu Z Q, Zhang H, Qiu F L. J Porous Mater, 2009, 16: 233
[32] Yuan X L, Zhang M, Chen X D, An N H, Liu G, Liu Y, Zhang W X, Yan W F, Jia M J. Appl Catal A, 2012, 439-440: 149
[33] Debecker D P, Stoyanova M, Rodemerck U, Leonard A, Su B L, Gaigneaux E M. Catal Today, 2011, 169: 60
[34] Debecker D P, Stoyanova M, Rodemerck U, Eloy P, Leonard A, Su B L, Gaigneaux E M. J Phys Chem C, 2010, 114: 18664
[35] Debecker D P, Stoyanova M, Rodemerck U, Gaigneaux E M. Stud Surf Sci Catal, 2010, 175: 581
[36] Braun S, Appel L G, Schmal M. Appl Surf Sci, 2002, 201: 227
[37] Wang C B, Cai Y P, Wachs I E. Langmuir, 1999, 15: 1223
[38] Balcar H, Mishra D, Marceau E, Carrier X, ?ilková N, Bastl Z. Appl Catal A, 2009, 359: 129
[39] Mariana A R L, Cedeno C L. Ind Eng Chem Res, 2011, 50: 2641
[40] Reddy B M, Reddy E P, Srinivas S T. J Catal, 1992, 136: 50
[41] Braun S, Appel L G, Camorim V L, Schmal M. J Phys Chem B, 2000, 104: 6584

热扩散法制备MoO₃/SiO₂催化草酸二甲酯和苯酚酯交换反应

Transesterification of dimethyl oxalate with phenol over a MoO₃/SiO₂ catalyst prepared by thermal spreading

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