硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响

doi:10.11949/j.issn.0438-1157.20171428

化工学报 ›› 2018, Vol. 69 ›› Issue (7): 3009-3017.DOI: 10.11949/j.issn.0438-1157.20171428

• 催化、动力学与反应器 • 上一篇下一篇

硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响

田海锋^1,2, 姚璐¹, 高佳良², 查飞¹, 郭效军¹

1 西北师范大学化学化工学院, 甘肃兰州 730070;
2 西北大学化工学院, 陕西西安 710069

收稿日期:2017-10-26 修回日期:2018-03-10 出版日期:2018-07-05 发布日期:2018-07-05
通讯作者: 査飞
基金资助:
西北师范大学青年教师提升计划项目（NWNU-LKQN-16-6）。

Effects of silylation and organic weak alkali modified Mo/HZSM-5 on catalytic performance in non-oxidative aromatization of methane reaction

TIAN Haifeng^1,2, YAO Lu¹, GAO Jialiang², ZHA Fei¹, GUO Xiaojun¹

1 College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China;
2 College of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, China

Received:2017-10-26 Revised:2018-03-10 Online:2018-07-05 Published:2018-07-05
Supported by:
supported by the Young Teacher Research Group Foundation of Northwest Normal University (NWNU-LKQN-16-6).

摘要/Abstract

摘要：

催化剂的形态及晶粒的组装对其催化性能有重要影响，采用硅烷化处理对Mo基催化剂表面酸性进行毒化制备了核壳型（Mo基催化剂@Silicalite-1）复合材料；采用四丙基氢氧化铵或正丁胺有机弱碱对Mo/HZSM-5进行刻蚀，然后经过脱硅再结晶分别制备了表面富硅型中空结构Mo/HZSM-5微球和表面富硅、核内含有多级孔道的Mo/HZSM-5微球。采用XRD、TEM、N₂等温吸脱附和NH₃-TPD对催化剂结构进行表征，并考察了三种不同后处理方法对Mo基催化剂在甲烷无氧芳构化反应中催化性能的影响。硅烷化和有机碱处理均能够调变Mo/HZSM-5催化剂的表面酸性，而经有机碱处理以后，催化剂结晶度、介孔比表面积和孔容均具有不同程度的增加，三种不同后处理方法均能改善Mo/HZSM-5催化剂的反应稳定性，对产物的分布也产生了显著影响。

关键词: 催化剂, 化学反应, 分子筛, 甲烷, 形貌结构

Abstract:

The morphology of catalysts and the assembly of catalysts particles have important influence on the catalytic performance. The core-shell composite materials with Mo/HZSM-5 as the core and silicalite-1 zeolite as shell were prepared by silylation. The hollow structure of Mo/HZSM-5 catalyst microspheres with rich silicon surface and hierarchical pore structure was prepared by the weak organic alkali etching method. The structure of Mo/HZSM-5 were characterized by XRD, TEM, N₂-adsorption-desorption and NH₃-TPD. The surface acidity of Mo/HZSM-5 catalysts was modulated by silylation or the weak organic alkali etching method. The crystallinity, mesoporous specific surface and pore volume of Mo/HZSM-5 catalyst increased by the weak organic alkali etching method. The catalytic performance of Mo/HZSM-5 catalysts via different post-treatment was investigated, the results show that the catalyst stability could be improved and the distribution of the product has a significant influence in non-oxidative aromatization of methane reaction.

Key words: catalyst, chemical reaction, molecular sieves, methane, morphological structure

中图分类号:

O643
TQ51

田海锋, 姚璐, 高佳良, 查飞, 郭效军. 硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响[J]. 化工学报, 2018, 69(7): 3009-3017.

TIAN Haifeng, YAO Lu, GAO Jialiang, ZHA Fei, GUO Xiaojun. Effects of silylation and organic weak alkali modified Mo/HZSM-5 on catalytic performance in non-oxidative aromatization of methane reaction[J]. CIESC Journal, 2018, 69(7): 3009-3017.

参考文献 33

[1]	WANG L S, TAO L X, XIE M S, et al. Dehydrogenation and aromatization of methane under non-oxidizing conditions[J]. Catal. Lett., 1993, 21(1):35-41.
[2]	苏玲玲. 甲烷在Mo基分子筛催化剂上的无氧芳构化反应:分子筛的酸性和孔结构作用的研究[D]. 大连:大连物理化学研究所, 2003. SU L L. Methane dehydroaromaitzaiton reaction on Mo-based catalyst:effect of the catalyst acid and porosity[D]. Dalian:Dalian Institute of Chemical Physics, 2003.
[3]	ABDELSAVED V, SHEKHAWAT D, SMITH M W. Effect of Fe and Zn promoters on Mo/HZSM-5 catalyst for methane dehydroaromatization[J]. Fuel, 2015, 139:401-410.
[4]	BUMS S, HARGREAVES J S J, PAL P, et al. The effect of dopants on the activity of MoO3/ZSM-5 catalysts for the dehydroaromatisation of methane[J]. Catal. Today, 2006, 114(4):383-387.
[5]	VOSMERIKOV A V, ZAIKOVSKⅡ V I, KOROBITSYNA L L, et al. Nonoxidative conversion of methane into aromatic hydrocarbons on Ni-Mo/ZSM-5 catalysts[J]. Kinet. Catal., 2009, 50(5):725-733.
[6]	ABOUL-GHEIT A K, AWADALLAH A E, ABOUL-ENEIN A A, et al. Molybdenum substitution by copper or zinc in H-ZSM-5 zeolite for catalyzing the direct conversion of natural gas to petrochemicals under non-oxidative conditions[J]. Fuel, 2011, 90(10):3040-3046.
[7]	LIU B S, JIANG L, SUN H, et al. XPS, XAES, and TG/DTA characterization of deposited carbon in methane dehydroaromatization over Ga-Mo/ZSM-5 catalyst[J]. Appl. Surf. Sci., 2007, 253(11):5092-5100.
[8]	ABOUL-GHEIT A K, AWADALLAH A E. Effect of combining the metals of group VI supported on H-ZSM-5 zeolite as catalysts for nonoxidative conversion of natural gas to petrochemicals[J]. J. Nat. Gas Chem., 2009, 18(1):71-77.
[9]	NGOBENI M W, CARLEY A F, SCURRELL M S, et al. The effects of boron and silver on the oxygen-free conversion of methane over Mo/H-ZSM-5 catalysts[J]. J. Mol. Catal. A:Chem., 2009, 305(1):40-46.
[10]	HASSAN A, SAYARI A. Highly active, selective and stable Mo/RuHZSM-5 catalysts for oxygen-free methane aromatization[J]. Appl. Catal. A:Gen., 2006, 297(2):159-164.
[11]	白杰, 刘盛林, 谢素娟, 等. Mg的添加对Mo/ZSM-5催化剂催化甲烷芳构化性能的影响[J]. 催化学报, 2004, 25(1):70-74. BAI J, LIU S L, XIE S J, et al. Effect of Mg addition on catalytic performance of Mo/ZSM-5 catalyst for methane aromatization[J]. Chin. J. Catal., 2004, 25(1):70-74.
[12]	苏玲玲, 马丁, 刘秀梅, 等. Re/HZSM-5体系上的甲烷无氧芳构化反应[J].催化学报, 2002, 23(1):41-45. SU L L, MA D, LIU X M, et al. Methane aromatization on Re/HZSM-5 system under non-oxygen condition[J]. Chin. J. Catal., 2002, 23(1):41-45.
[13]	DING W P, MEITZNER G D, IGLESIA E. The effects of silanation of external acid sites on the structure and catalytic behavior of Mo/HZSM5[J]. J. Catal., 2002, 206(1):14-22.
[14]	WANG H X, HU G, LEI H, et al. A facile and effective method for the distribution of Mo-HZSM-5 catalyst active centers[J]. Catal. Lett., 2003, 89(1):75-79.
[15]	刘红梅, 申文杰, 刘秀梅,等. 分子筛的酸处理对Mo/HZSM-5催化甲烷无氧芳构化反应性能的影响[J]. 催化学报, 2004, 25(9):688-692. LIU H M, SHEN W J, LIU X M, et al. Effect of acid treatment of zeolite on catalytic performance of Mo/HZSM-5 for methane dehydroaromatization[J]. Chin. J. Catal., 2004, 25(9):688-692.
[16]	SU L L, LIU L, ZHUANG J Q, et al. Creating mesopores in ZSM-5 zeolite by alkali treatment:a new way to enhance the catalytic performance of methane dehydroaromatization on Mo-HZSM-5 catalysts[J]. Catal. Lett., 2003, 91(3):155-167.
[17]	YANG J, YU S, HU H N. et al. Synthesis of hierarchical HZSM-5 microspheres without second template and their application in methane dehydroaromatization[J]. Chinese J. Catal., 2011, 32:362-367.
[18]	CHU N, WANG J, ZHANG Y, et al. Nestlike hollow hierarchical MCM-22 microspheres:synthesis and exceptional catalytic properties[J]. Chem. Mater., 2010, 22:2757-2763.
[19]	CUI Y B, XU Y B, SUZUKI Y, et al. Experimental evidence for three rate-controlling regions of the non-oxidative methane dehydroaromatization over Mo/HZSM-5 catalyst at 1073 K[J]. Catal. Sci. Technol., 2011, 1(5):823-829.
[20]	DAI C Y, ZHANG A F, LIU M, et al. Hollow ZSM-5 with silicon -rich surface, double shells, and functionalized interior with metallic nanoparticles and carbon nanotubes[J]. Adv. Funct. Mater., 2016, 25(48):7479-7487.
[21]	DAI C Y, ZHANG A F, LI L L, et al. Synthesis of hollow nanocubes and macroporous monoliths of silicalite-1 by alkaline treatment[J]. Chem. Mater., 2013, 25(21):4197-4205.
[22]	ISMAGILOV Z R, MATUS E V, TSIKOZA L T. Direct conversion of methane on Mo/ZSM-5 catalysts to produce benzene and hydrogen:achievements and perspectives[J]. Energ. Environ. Sci., 2008, 1(5):526-541.
[23]	郭春垒, 王银斌, 汪洋, 等. 硅烷化改性对纳米ZSM-5甲醇制汽油催化剂性能的影响[J]. 分子催化, 2016, 30(2):115-122. GUO C L, WANG Y B, WANG Y, et al. The effect of silylation on the catalytic performance of nanosize ZSM-5 zeolites for the conversion of methanol to gasoline[J]. Mol. Catal., 2016, 30(2):115-122.
[24]	SAR1O?LAN A, SAVA?Ç1 T Ö, ERDEM-?ENATALAR A, et al. The effect of support morphology on the activity of HZSM-5-supported molybdenum catalysts for the aromatization of methane[J]. J. Catal., 2007, 246(1):35-39.
[25]	MOTUZAS J, JULBE A, NOBLE R D, et al. Rapid synthesis of silicalite-1 seeds by microwave assisted hydrothermal treatment[J]. Micropor. Mesopor. Mat., 2005, 80(1):73-83.
[26]	QIN Z X, MELINTE G, GILSON J P M, et al. The mosaic structure of zeolite crystals[J]. Angew. Chem. Int. Edit., 2016, 55(48):15049-15052.
[27]	MEI C S, LIU Z C, WEN P Y, et al. Regular HZSM-5 microboxes prepared via a mild alkaline treatment[J]. J. Mater. Chem., 2008, 18(29):3496-3500.
[28]	MARTÍNEZ A, PERIS E, DEREWINSKI M, et al. Improvement of catalyst stability during methane dehydroaromatization (MDA) on Mo/HZSM-5 comprising intracrystalline mesopores[J]. Catal. Today, 2011, 169(1):75-84.
[29]	MA D, LV Y, SU L L, et al. Remarkable improvement on the methane aromatization reaction:a highly selective and coking-resistant catalyst[J]. J. Phys. Chem. B, 2002, 106(34):8524-8530.
[30]	HU J, WU S J, LI Z F, et al. Nano-MoO3-modified MCM-22 for methane dehydroaromatization[J]. Appl. Organomet. Chem., 2015, 29(9):638-645.
[31]	LIU H M, LI Y, SHEN W J, et al. Methane dehydroaromatization over Mo/HZSM-5 catalysts in the absence of oxygen:effects of silanation in HZSM-5 zeolite[J]. Catal. Today, 2004, 93/94/95:65-73.
[32]	TEMPELMAN C H L, DE RODRIGUES V O, VAN ECK E R H, et al. Desilication and silylation of Mo/HZSM-5 for methane dehydroaromatization[J]. Micropor. Mesopor. Mat., 2015, 203:259-273.
[33]	LU Y, MA D, XU Z S, et al. A high coking-resistance catalyst for methane aromatization[J]. Chem. Commun., 2001, (20):2048-2049.

硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响

Effects of silylation and organic weak alkali modified Mo/HZSM-5 on catalytic performance in non-oxidative aromatization of methane reaction

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[2]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[3]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[4]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[5]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[6]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[7]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[8]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[9]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[10]	牛超, 沈胜强, 杨艳, 潘泊年, 李熠桥. 甲烷BOG喷射器流动过程计算与性能分析[J]. 化工学报, 2023, 74(7): 2858-2868.
[11]	何晓崐, 刘锐, 薛园, 左然. MOCVD生长AlN单晶薄膜的气相和表面化学反应综述[J]. 化工学报, 2023, 74(7): 2800-2813.
[12]	刘晓洋, 喻健良, 侯玉洁, 闫兴清, 张振华, 吕先舒. 螺旋微通道对掺氢甲烷爆轰传播的影响[J]. 化工学报, 2023, 74(7): 3139-3148.
[13]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[14]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.
[15]	周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.