硼酸改性MCM-22分子筛催化甲苯烷基化合成对二甲苯

doi:10.16085/j.issn.1000-6613.2017.06.030

化工进展 ›› 2017, Vol. 36 ›› Issue (06): 2177-2182.DOI: 10.16085/j.issn.1000-6613.2017.06.030

硼酸改性MCM-22分子筛催化甲苯烷基化合成对二甲苯

薛冰, 吴浩, 文琳智, 柳娜, 李永昕

常州大学石油化工学院, 江苏省绿色催化材料与技术重点实验室, 江苏常州 213164

收稿日期:2016-10-18 修回日期:2017-01-18 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 薛冰
作者简介:薛冰(1978—),男,博士,副研究员。E-mail:xuebing@cczu.edu.cn。
基金资助:
国家自然科学基金（21076027）、江苏省绿色催化材料与技术重点实验室项目（BM2012110）及江苏省先进催化和绿色制造协同创新项目（ACGM2016-06-29）。

Synthesis of p-xylene by alkylation of toluene over boric acid modified MCM-22 zeolite catalysts

XUE Bing, WU Hao, WEN Linzhi, LIU Na, LI Yongxin

School of Petrochemical Engineering, Changzhou University, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou 213164, Jiangsu, China

Received:2016-10-18 Revised:2017-01-18 Online:2017-06-05 Published:2017-06-05

摘要/Abstract

摘要： 以硼酸为前体、低碳脂肪醇为溶剂，通过浸渍法制备了一系列硼酸改性MCM-22微孔分子筛择形催化剂，在连续流动固定床反应器上考察了甲苯与碳酸二甲酯烷基化合成对二甲苯的择形催化性能。通过XRD、FTIR、N₂吸附脱附、NH₃-TPD、吡啶吸附FTIR等手段对催化剂进行表征，并通过异丙苯和1，3，5-三异丙苯的裂解反应考察了硼酸改性对MCM-22微孔分子筛催化剂的内、外表面酸性质的影响。实验结果表明：以硼酸为前体、正丙醇为溶剂制备的硼改性MCM-22催化剂在甲苯与碳酸二甲酯烷基化合成对二甲苯过程中不仅表现出优异的择形性能，而且还保持了较高的催化活性。这可能是由于在浸渍过程中，硼酸与正丙醇反应生成分子尺寸较大的有机硼酸酯，从而实现了在覆盖分子筛外表面酸性位的同时不影响其孔内酸性质。

关键词: 催化, 固定床, 对二甲苯, 硼酸, 脂肪醇, 沸石, MCM-22

Abstract: A series of boric acid modified MCM-22 catalysts were prepared by impregnation method with boric acid as the precursor and fatty alcohol as the solvent. The catalytic performance of the boric acid modified MCM-22 catalysts in the synthesis of p-xylene(PX)by alkylation of toluene with dimethyl carbonate(DMC)was investigated on a fixed bed reactor. The catalysts were characterized by means of XRD,FTIR,N₂ adsorption desorption,NH₃-TPD,and FTIR with pyridine adsorption. Furthermore,the effects of boric acid modification on the acid property of MCM-22 zeolite were also investigated through the cracking reactions of cumene and 1,3,5-triisopropylbenzene. The results indicated that the prepared catalysts with 1-propanol as the solvent exhibited both excellent shape-selectivity and high catalytic activity in the synthesis of PX. This should be ascribed to the formation of organic borate during the impregnation process by the reaction of boric acid and 1-propanol,which achieved good coverage of the acid sites on the external surface of MCM-22 zeolite while preserve the acid sites inside the pores .

Key words: catalysis, fixed-bed, p-xylene, boric acid, fatty alcohol, zeolite, MCM-22

中图分类号:

TQ241.1

薛冰, 吴浩, 文琳智, 柳娜, 李永昕. 硼酸改性MCM-22分子筛催化甲苯烷基化合成对二甲苯[J]. 化工进展, 2017, 36(06): 2177-2182.

XUE Bing, WU Hao, WEN Linzhi, LIU Na, LI Yongxin. Synthesis of p-xylene by alkylation of toluene over boric acid modified MCM-22 zeolite catalysts[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2177-2182.

参考文献

[1] 丰存礼. 我国对二甲苯行业分析及发展建议[J]. 化工进展,2013,32(8):1988-1993. FENG C L. PX industry and proposal for its development in China[J]. Chemical Industry and Engineering Progress,2013,32(8):1988-1993.
[2] 孔德金,杨为民. 芳烃生产技术进展[J]. 化工进展,2011,30(1):16-25. KONG D J,YANG W M. Advance in technology for production of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress,2011,30(1):16-25.
[3] TSAI T C,LIU S B,WANG I. Disproportionation and transalkylation of alkylbenzenes over zeolite catalysts[J]. Applied Catalysis A:General,1999,181(2):355-398.
[4] 李永昕,吴润泽,薛冰. HMCM-22/MCM-41的制备及其在甲苯碳酸二甲酯烷基化中的催化性能[J]. 化工进展,2010,29(5):875-879. LI Y X,WU R Z,XUE B. Synthesis of HMCM-22/MCM-41 and catalytic performance for toluene alkylation with dimethyl carbonate[J]. Chemical Industry and Engineering Progress,2010,29(5):875-879.
[5] SOTELO J L,UGUINA M A,VALYERDE J L,et al. Deactivation kinetics of toluene alkylation with methanol over magnesium-modified ZSM-5[J]. Industrial & Engineering Chemistry Research,1996,35(4):1300-1306.
[6] INAGAKI S,KAMINO K,KIKUCHI E,et al. Shape selectivity of MWW-type aluminosilicate zeolites in the alkylation of toluene with methanol[J]. Applied Catalysis A,2007,318(7):22-27.
[7] ZHU Z,CHEN Q,XIE Z,et al. The roles of acidity and structure of zeolite for catalyzing toluene alkylation with methanol to xylene[J]. Microporous & Mesoporous Materials,2006,88(1):16-21.
[8] ZHAO Y,TAN W,WU H,et al. Effect of Pt on stability of nano-scale ZSM-5 catalyst for toluene alkylation with methanol into p-xylene[J]. Catalysis Today,2011,160(1):179-183.
[9] KIM J H,ISHIDA A,OKAJIMA M,et al. Modification of HZSM-5 by CVD of various silicon compounds and generation of para-selectivity[J]. Journal of Catalysis,1996,161(1):387-392.
[10] ZHU Z,CHEN Q,XIE Z,et al. Shape-selective disproportionation of ethylbenzene to para-diethylbenzene over ZSM-5 modified by chemical liquid deposition and MgO[J]. Journal of Molecular Catalysis A:Chemical,2006,248(1/2):152-158.
[11] BAUER F,CHEN W H,BILZ E,et al. Surface modification of nano-sized HZSM-5 and HFER by pre-coking and silanization[J]. Journal of Catalysis,2007,251(2):258-270.
[12] 李永昕,邓丽君,薛冰. 甲苯与碳酸二甲酯择形烷基化合成对二甲苯[J]. 化工进展,2010,29(4):665-669. LI Y X,DENG L J,XUE B. Selective synthesis of p-xylene by alkylation of toluene with dimethyl carbonate[J]. Chemical Industry and Engineering Progress,2010,29(4):665-669.
[13] 王永飞,薛冰,许杰,等. 乙酸镁改性ZSM-5 分子筛上甲苯与碳酸二甲酯的择形烷基化[J]. 化工进展,2011,30(7):1498-1502. WANG Y F,XUE B,XU J,et al. Selective synthesis of p-xylene by alkylation of toluene with dimethyl carbonate over magnesium acetate-modified ZSM-5[J]. Chemical Industry and Engineering Progress,2011,30(7):1498-1502.
[14] 冯益庆,陈连璋. 硼酸水溶液处理对HZSM-5沸石催化剂催化性能的影响[J]. 石油学报(石油加工),1991(2):44-51. FENG Y Q,CHEN L Z. The effects of boric acid aqueous solution modification on the catalytic performances of HZSM-5 zeolites[J]. Acta Petrolei Sinica(Petroleum Processing Section),1991(2):44-51.
[15] BING X,ZHANG G,NA L,et al. Highly selective synthesis of para-diethylbenzene by alkylation of ethylbenzene with diethyl carbonate over boron oxide modified HZSM-5[J]. Journal of Molecular Catalysis A:Chemical,2014,395:384-391.
[16] 王振东,张云贤,张斌,等. 不同形貌MCM-22分子筛的合成及其催化性能[J]. 石油学报(石油加工),2014,30(2): 110-114. WANG Z D,ZHANG Y X,ZHANG B,et al. Synthesis and catalytic properties of MCM-22 zeolites with different morphologies[J]. Acta Petrolei Sinica(Petroleum Processing Section),2014,30(2):110-114.
[17] PARALA H,WINKLER H,KOLBE M,et al. Confinement of CdSe nanoparticles inside MCM-41[J]. Advanced Materials,2000,12(14):1050-1055.
[18] ARDELEAN I,CORA S,LUCACEL R C,et al. EPR and FT-IR spectroscopic studies of B₂O₃,Bi₂O₃,MnO glasses[J]. Solid State Sciences,2005,7(11):1438-1442.
[19] WU P,KOMATSU T,YASHIMA T. Selective formation of p-xylene with disproportionation of toluene over MCM-22 catalysts[J]. Microporous and Mesoporous Materials,1998,22(1-3):343-356.
[20] 葛春华,李鸿图. 硼酸酯的合成与应用[J]. 辽宁化工,1999,28(2):90-92. GE C H,LI H T. Synthesis and application of boric acid ester[J]. Liaoning Chemical Industry,1999,28(2):90-92.
[21] ROBERT M W,EMESTL L,CHARLES F A,et al. Preparation,properties,and uses of borate esters[J]. Advances in Chemistry,1959,23:129-157.
[22] 柯以侃,董慧茹. 分析化学手册:光谱分析[M]. 2版. 北京:化学工业出版社,1998:968. KE Y K,DONG H R. Handbook of analytical chemistry:spectral analysis[M]. 2nd Edition. Beijing:Chemical Industry Press,1998:968.

硼酸改性MCM-22分子筛催化甲苯烷基化合成对二甲苯

Synthesis of p-xylene by alkylation of toluene over boric acid modified MCM-22 zeolite catalysts

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[7]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[8]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[9]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[10]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[11]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[12]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[13]	董佳宇, 王斯民. 超声强化对二甲苯结晶特性及调控机理实验[J]. 化工进展, 2023, 42(9): 4504-4513.
[14]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[15]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.