丙烷芳构化催化剂活性组分浸渍方法优化

doi:10.11949/j.issn.0438-1157.20170505

摘要/Abstract

摘要：

根据现有丙烷芳构化催化剂的特性，考察等体积浸渍、真空等体积浸渍、微波等体积浸渍3种不同浸渍方法对镓改性HZSM-5催化剂性能的影响，并结合多种技术表征，分析改性后催化剂内部性能变化情况。研究发现，浸渍方法对催化剂表面镓的分散度具有明显的影响，其中真空等体积浸渍具有更好的效果，使活性组分Ga分散更均匀，更有效地降低了分子筛的B酸位、增加了L酸位，进而抑制了丙烷的裂解，增强了催化剂的脱氢、芳构化能力，并且延长了催化剂的寿命。在反应温度为525℃，丙烷质量空速（WHSV）为1 h^-1的条件下，取样时间为丙烷通入后1.3 h，丙烷转化率达到93.8%，液相芳烃收率达到57.2%，BTX（苯、甲苯和二甲苯）收率达到48.6%。

关键词: 分子筛, 镓, 烷烃, 真空等体积浸渍, 脱氢, 裂解, 选择性

Abstract:

Based on the current understanding of the nature of the propane aromatization catalyst,the catalytic activity of Ga modified HZSM-5 prepared by different impregnation methods is studied,including incipient wetness,vacuum assisted incipient wetness,and microwave assisted incipient wetness impregnations. With the help of various catalyst characterization techniques,the microscopic changes of the catalysts after modification were examined. The result showed that methods of impregnation had significant effects over dispersion of Ga species on the surface of the catalysts where vacuum assisted impregnation was proved to have the best results. At reaction temperature of 525℃,propane WHSV=1 h^-1,product sampled after 1.3 h of propane on stream time suggested a propane conversion of 93.8%,liquid aromatization yield of 57.2% and BTX yield of 48.6%. Vacuum assisted impregnation methods led to better Ga distribution thereby reduced B acid sites and increased L acid sites. This modification resulted in inhibited propane cracking,increased dehydrogenation and aromatization reactions,as well as a longer catalyst life.

Key words: molecular sieve, Ga, alkane, vacuum assisted incipient wetness impregnation, dehydrogenation, cracking, selectivity

中图分类号:

TQ028.8

何霖, 程牧曦, 潘相米, 王科, 谭亚南, 韩伟, 艾珍. 丙烷芳构化催化剂活性组分浸渍方法优化[J]. 化工学报, 2017, 68(S1): 204-209.

HE Lin, CHENG Muxi, PAN Xiangmi, WANG Ke, TAN Yanan, HAN Wei, AI Zhen. Optimization of impregnation methods for propane aromatization catalyst[J]. CIESC Journal, 2017, 68(S1): 204-209.

参考文献 30

[1]	ROBIN J N,MARK E D,CYRIL T O'C. Aromatization of 1-hexane and 1-octene by gallium/H-ZSM-5 catalysts[J]. Applied Catalysis A:General,1996,134(2):285-297.
[2]	VASANT R C,PANJALA D,SUBHABRATA B,et al. Aromatization of dilute ethylene over Ga-modified ZSM-5 type catalysts[J]. Microporous and Mesoporous Materials,2001,47(2/3):253-267.
[3]	GUISNET M,GNEP N S,ALARIO F. Aromatization of short chain alkanes on zeolite catalysts[J]. Cheminform,1992,89(92):1-30.
[4]	CHEN N Y,YAN T Y. M2 forming-a process for aromatization of light hydrocarbons[J]. Industrial & Engineering Chemistry Process Design & Development,1986,25:1.
[5]	YOSHIO O. Transformation of lower alkanes into aromatic hydrocarbons over ZSM-5 zeolites[J]. Catalysis Reviews,1992,34(3):179-226.
[6]	GIUSEPPE G,REINALDO M,ROBERTO G. Transformation of LPG into aromatic hydrocarbons and hydrogen over zeolite catalysts[J]. Catalysis Reviews Science & Engineering,1994,36(2):271-304.
[7]	NARAYANAN S,SULTANA A,KRISHNA K,et al. Synthesis of ZSM-5 type zeolites with and without template and evaluation of physicochemical properties and aniline alkylation activity[J]. Catalysis Letters,1995,34.
[8]	KWAK B S,SACHTLER W M H. Characterization and testing of Ga/HZSM-5 prepared by sublimation of GaCl3 into HZSM-5[J]. Journal of Catalysis,1993,141(2):729-732.
[9]	BUCKLES G J,HUTCHINGS G J. Aromatization of propane over Ga/HZSM-5:comments on the activation of propane[J]. Catalysis Today,1996,(31):233-246.
[10]	DEROUANE E G,HAMID S B A,IVANOVA I I,et al. Thermodynamic and mechanistic studies of initial stages in propane aromatisation over Ga-modified H-ZSM-5 catalysts[J]. Journal of Molecular Catalysis,1994,86(93):371-400.
[11]	BAYENSE C R. Aromatization of propane over MFI-gallosilicates[J]. Applied Catalysis,1991,72(1):81-98.
[12]	CHOUDHARY V R,MANTRI K,SIVADINARAYANA C. Influence of zeolite factors affecting zeolitic acidity on the propane aromatization activity and selectivity of Ga/H-ZSM-5[J]. Microporous & Mesoporous Materials,2000,37(1):1-8.
[13]	CARLI R,RAGAINI V. Catalytic activity of a mechanically mixed Ga2O3/H-MFI catalyst under distance preservative conditions[J]. Catalysis Today,1996,31(3/4):257-264.
[14]	KANAZIREV V,DIMITROVA R,PRICE G L,et al. IR study of the active sites formed by H2 treatment of Ga/HZSM-5 catalysts[J]. Journal of Molecular Catalysis,1991,70(91):111-117.
[15]	MEITZNER G D, IGLESIA E, BAUMGARTNER J E,et al. The chemical state of gallium in working alkane dehydrocyclodimerization catalysts. In situ gallium K-edge X-ray absorption spectroscopy[J]. Journal of Catalysis,1993,140:209-225.
[16]	KANAZIREV V,PIFFER R,FOSTER H. FTIR spectroscopic evidence for a key role of hydrogen in creating an active state of Ga2O3/HZSM-5 mixed catalysts[J]. Journal of Molecular Catalysis,1991,69(2):L15-L18.
[17]	KWAK B S,SACHTLER W M H,HAAG W O. ChemInform abstract:catalytic conversion of propane to aromatics:effects of adding Ga and/or Pt to HZSM-5[J]. Cheminform,1995,26(11),DOI:10.1002/chin.199511062
[18]	张舜光,董群,刘林林,等. 芳构化催化剂研究进展[J]. 天津化工,2006,20(3):23-26. ZHANG S G,DONG Q,LIU L L,et al. The development of aromatization catalyst[J]. Tianjin Chemical Industry,2006,20(3):23-26.
[19]	宋月芹. 液化气中烯烃芳构化制取高辛烷值汽油的研究[D]. 大连:中国科学院大连化学物理研究所,2005. SONG Y Q. Study on aromatization of alkene in LPG to synthesize high octane gasoline[D]. Dalian:Dalian Institute of Chemical Physics,Chinese Academy of Sciences,2005.
[20]	叶娜. 纳米ZSM-5沸石上C4液化气低温芳构化反应研究[D]. 大连:大连理工大学,2006. YE N. Studyonthe low-temperature aromatization of C4 liquified petroleum gas over nano-sized ZSM-5 zeolite[D]. Dalian:Dalian University of Technology,2006.
[21]	周建宏,赵云,宋金富,等.改性纳米HZSM-5沸石催化剂上C5~C8混合烷烃的芳构化反应[J]. 催化学报,2008,(7):665-670. ZHOU J H,ZHAO Y,SONG J F,et al. Aromatization of C5-C8 alkane mixture over modified nano-sized HZSM-5 zeolite catalysts[J]. Chinese Journal of Catalysis,2008,(7):665-670.
[22]	赵云. 改性纳米ZSM-5沸石上C5~C8链烷烃芳构化反应的研究[D]. 大连:大连理工大学,2009. ZHAO Y. Aromatization of C5-C8 paraffins over modified nano-sized ZSM-5 zeolite[D]. Dalian:Dalian University of Technology,2009.
[23]	程谟杰,杨亚书. ZnHZSM-5上脱氮环化芳构化过程的探讨[J]. 分子催化,1996,10(6):418-422. CHENG M J,YANG Y S. Study on dehydrocyclization and aromatization process over ZnHZSM-5 catalyst[J]. Journal of Molecular Catalysis,1996,10(6):418-422.
[24]	尹双凤,陈懿,林洁,等. 正己烷在Zn/HZSM-5上芳构化反应机理的探讨[J]. 工业催化,2002,10(1):33-37. YIN S F,CHEN Y,LIN J,et al. An investigation on mechanism for aromatization of n-hexane on Zn/HZSM-5 catalyst[J]. Industrial Catalysis,2002,10(1):33-37.
[25]	王军威,张志新,王心葵. Zn/HZSM-5分子筛催化剂对丙烷芳构化反应中芳烃分布的影响[J]. 分子催化,2000,14(1):15-19. WANG J W,ZHANG Z X,WANG X K. Effect of aromatics distribution in aromatization of propane over Zn/HZSM-5 zeolite catalysts[J]. Journal of Molecular Catalysis,2000,14(1):15-19.
[26]	涂先红,方向晨,赵乐平,等. C6~C8烃类转化及芳构化反应机理的研究[J]. 工业催化,2007,15(1):19-23. TU X H,FANG X C,ZHAO L P,et al. Studies onmechanism for conversion and aromatization of C6-C8 hydrocarbons[J]. Industrial Catalysis,2007,15(1):19-23.
[27]	栾春晖,卢学栋,韩怡卓. 烃类在HZSM-5-Zn和HZSM-5上芳构化反应及动力学考察[J]. 天然气化工,1994,19(5):20-22. LUAN C H,LU X D,HAN Y Z. Investigation on aromatization of hydrocarbons over HZSM-5 and ZnHZSM-5 and its kinetics[J]. Natural Gas Chemical Industry,1994,19(5):20-22.
[28]	李牛,朱瑞芝,潘履让. 第二改性物对ZnHZSM-5催化正戊烷芳构化反应的影响[J]. 工业催化,1997,(3):27-31. LI N,ZHU R Z,PAN L R. Effectof second modifying oxide on ZnHZSM-5 catalyst for n-pentane aromatization[J]. Industrial Catalysis,1997,(3):27-31.
[29]	郝代军,朱建华,王国良,等. 液化石油气制芳烃技术开发及工业应用[J]. 现代化工,2006,26(10):55-60. HAO D J,ZHU J H,WANG G L,et al. Technological development and commercial application of liquefied petroleum gasin aromatics[J]. Mordern Chemical Industry,2006,26(10):55-60.
[30]	赵晨曦,宋春敏,阎子峰. NiO改性HZSM-5分子筛催化剂催化1-丁烯芳构化反应[J]. 石油化工,2005,34(10):917-921. ZHAO C X,SONG C M,YAN Z F. 1-Butenearomatization on NiO-modified HZSM-5 molecular sieve catalyst[J]. Petrochemical Technology,2005,34(10):917-921.

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