Volume 43 Issue 08
Aug.  2015
Turn off MathJax
Article Contents
LIU Ru-ling, ZHU Hua-qing, WU Zhi-wei, QIN Zhang-feng, FAN Wei-bin, WANG Jian-guo. Aromatization of propane over Ga-modified ZSM-5 catalysts[J]. Journal of Fuel Chemistry and Technology, 2015, 43(08): 961-969.
Citation: LIU Ru-ling, ZHU Hua-qing, WU Zhi-wei, QIN Zhang-feng, FAN Wei-bin, WANG Jian-guo. Aromatization of propane over Ga-modified ZSM-5 catalysts[J]. Journal of Fuel Chemistry and Technology, 2015, 43(08): 961-969.

Aromatization of propane over Ga-modified ZSM-5 catalysts

  • Received Date: 2015-03-31
  • Rev Recd Date: 2015-05-12
  • Publish Date: 2015-08-30
  • H-ZSM-5 was modified with gallium by the ion-exchange method and characterized with XRD, SEM, BET, NH3-TPD, Py-IR, ICP, and XPS techniques. The influences of the Si/Al mol ratios and the pretreatment conditions of the Ga-modified ZSM-5 ((Ga-H)-ZSM-5) on their acidity, gallium species state, and aromatization performance of propane were investigated. It was found that the Si/Al mol ratio had significant effects on the catalyst acidity and the interaction of non-framework Ga species with zeolite, and hence, the catalytic activity and selectivity for propane aromatization. At 550℃ and WHSV of 1.0h-1, (Ga,H)-ZSM-5 with a Si/Al mol ratio of 30 showed the highest catalytic activity. It was shown that Ga species improved the aromatics selectivity and inhibited cracking reactions. After being reduced in hydrogen, Ga2O3 was most likely transformed into Ga+ and GaH+2 species, and migrated into the zeolite channels. Subsequent air-oxidation treatment of the reduced (Ga,H)-ZSM-5 led to formation of GaO+ species, thus greatly increasing the aromatization activity.
  • loading
  • ONO Y. Transformation of lower alkanes into aromatic hydrocarbons over ZSM-5 zeolites[J]. Catal Rev: Sci Eng, 1992, 34(3): 179-226.
    DEHERTOG W J H, FROMEN G F. A catalytic route for aromatics production from LPG[J]. Appl Catal A: Gen, 1999, 189(1): 63-75.
    BHAN A, DELGASS W N. Propane aromatization over HZSM-5 and Ga/HZSM-5 catalysts[J]. Catal Rev: Sci Eng, 2008, 50(1): 19-151.
    CHOUDHARY V R, KINAGE A K, SIVADINARAYANA C, GUISNET M. Pulse reaction studies on variations of initial activity/selectivity of O2 and H2 pretreated Ga-modified ZSM-5 type zeolite catalysts in propane aromatization[J]. J Catal, 1996, 158(1): 23-33.
    CHOUDHARY T V, KINAGA A, BANERJEE S, CHOUDHARY V R. Influence of Si/Ga and Si/Al ratios on propane aromatization over highly active H-GaAlMFI[J].Catal Comm, 2006, 7(3): 166-169.
    GUISNET M, GNEP N S. Aromatization of short chain alkanes on zeolite catalysts[J]. Appl Catal A: Gen, 1992, 89(1): 1-30.
    NOWAK I, QUARTARARO J, DEROUANE E G, VEDRINE J C. Effect of H2-O2 pre-treatments on the state of gallium in Ga/H-ZSM-5 propane aromatisation catalysts[J]. Appl Catal A: Gen, 2003, 251(1): 107-120.
    ANUNZIATA O A, PIERELLA L B. Nature of the active sites in H-ZSM-11zeolite modified with Zn(2+) and Ga(3+)[J]. Catal Lett, 1993, 19(2/3): 143-151.
    苗青, 董梅, 牛宪军, 王浩, 樊卫斌, 王建国, 秦张峰. 含镓ZSM-5 分子筛的制备及其在甲醇芳构化反应中的催化性能[J]. 燃料化学学报, 2012, 40(10): 1230-1238. (MIAO Qing, DONG Mei, NIU Xian-jun, WANG Hao, FAN Wei-bin, WANG Jian-guo, QIN Zhang-feng. Synthesis of gallium-containing ZSM- 5 molecular sieves and their catalytic performance in methanol aromatization[J]. J Fuel Chem Technol, 2012, 40(10): 1230-1238.)
    DOOLEY K M, CHANG C, PRICE G L. Effects of pretreatments on state of gallium and aromatization activity of gallium/ZSM-5 catalysts[J]. Appl Catal A: Gen, 1992, 84(1): 17-30.
    PRICE G L, KANAZIREV V. Ga2O3/HZSM-5 propane aromatization catalysts: Formation of active centers via solid-state reaction[J]. J Catal, 1990, 126(1): 267-278.
    MADEIRA F F, TAYEB K B, PINARD L, VEZIN H, MAURY S, CADRAN N. Ethanol transformation into hydrocarbons on ZSM-5 zeolites: Influence of Si/Al ratio on catalytic performances and deactivation rate. Study of the radical species role[J]. Appl Catal A: Gen, 2012, 443-444: 171-180.
    朱华青, 翟效珍, 王建国. 第二组分改性Ga/HZSM-5催化剂芳构化性能研究[J]. 燃料化学学报, 1999, 27(S): 74-78. (ZHU Hua-qing, ZHAI Xiao-zhen, WANG Jian-guo. Study on aromatization over Ga/HZSM-5 catalysts modified by second components[J]. J Fuel Chem Technol, 1999, 27(S): 74-78.)
    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 Mater, 2000, 37(1/2): 1-8.
    HAAG W O, LAGO R M, WEISZ P B. The active-site of acidic aluminosilicate catalysts[J]. Nature, 1984, 309(5969): 589-591.
    HENSEN E J M, GARCIA-SANCHEZ M, RANE N, MAGUSIN P C M M, LIU P H, CHAO K J, VAN SANTEN R A. In situ Ga K edge XANES study of the activation of Ga/ZSM-5 prepared by chemical vapor deposition of trimethylgallium[J]. Catal Lett, 2005, 101(1/2): 79-85.
    KAZANSKY V B, SUBBOTINA I R, SANTEN R A, HENSEN E J M. DRIFTS study of the chemical state of modifying gallium ions in reduced Ga/ZSM-5 prepared by impregnation: I. Observation of gallium hydrides and application of CO adsorption as a molecular probe for reduced galliumions[J]. J Catal, 2004, 227(2): 263-269.
    高志贤, 程昌瑞, 谭长谕. Ga/HZSM-5催化剂中镓的状态及其分布的XPS研究[J].燃料化学学报, 1995, 23(3): 301-305. (GAO Zhi-xian, CHENG Chang-rui, TAN Chang-yu. XPS study on state and distribution of gallium in Ga/HZSM-5 catalyst[J]. J Fuel Chem Technol,1995, 23(3): 301-305.)
    RANE N, OVERWEG A R, KAZANSKY V B, SANTEN R A V, HENSEN E J M. Characterization and reactivity of Ga+ and GaO+ cations in zeolite ZSM-5[J]. J Catal, 2006, 239(2): 478-485.
    王恒强, 张成华, 吴宝山, 任杰, 李永旺. Ga、Zn改性方法对HZSM-5催化剂丙烯芳构化性能的影响[J]. 燃料化学学报, 2010, 38(3): 576-581. (WANG Heng-qiang, ZHANG Cheng-hua, WU Bao-shan, REN Jie, LI Yong-wang. Effect of Ga and Zn modification on propylene aromatization over HZSM-5 catalysts[J]. J Fuel Chem Technol, 2010, 38(3): 576-581.)
    MONTES A, GIANNETTOB G. A new way to obtain acid or bifunctional catalysts V. Considerations on bifunctionality of the propane aromatizationreaction over-ZSM-5 catalysts[J]. Appl Catal A: Gen, 2000, 197(1): 31-39.
    PIDKO E A, HENSEN E J M, VAN SANTEN R A. Dehydrogenation of light alkanes over isolated gallyl ions in Ga/ZSM-5 zeolites[J]. J Phys Chem, 2007, 111(35): 13068-13075.
    AUSAVASUKHI A, SOOKNOI T. Tunable activity of HZSM-5 with H2 treatment: Ethane dehydrogenation[J]. Catal Comm, 2014, 45(1): 63-68.
  • 加载中

Catalog

    通讯作者: 陈斌, bchen63@163.com
    • 1. 

      沈阳化工大学材料科学与工程学院 沈阳 110142

    1. 本站搜索
    2. 百度学术搜索
    3. 万方数据库搜索
    4. CNKI搜索

    Article Metrics

    Article views (528) PDF downloads(465) Cited by()
    Proportional views
    Related

    /

    DownLoad:  Full-Size Img  PowerPoint
    Return
    Return