Citation:
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]. Journal of Fuel Chemistry and Technology,
;2012, 40(10): 1230-1239.
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Gallium species were introduced into ZSM-5 molecular sieves through three different measures, i.e. hydrothermal synthesis, impregnation, and ion exchange. The gallium-containing ZSM-5 molecular sieves were characterized by XRD, SEM, FT-IR, NH3-TPD, ICP, XPS and N2 sorption. The effects of silica source and the content and state of gallium species on their structure, acid property, and catalytic performance in the aromatization of methanol were investigated. The results indicated that the silica source (silica white, tetraethyl orthosilicate, and silica sol) exhibits significant effects on the crystal size and the state of gallium species, and thus influences the catalytic activity and stability of the gallium-containing ZSM-5 molecular sieves in methanol aromatization considerably. There are three kinds of gallium species, i.e. framework Ga, Ga2O3 species on the crystal surface, and non-framework Ga species with strong interaction with the framework oxygen. The framework gallium species in the tetrahedral structure offers the acidic sites of the molecular sieves, while the non-framework gallium acts as the active sites for methanol aromatization. The proper amounts of non-framework gallium species matched with the acid sites can promote the formation of aromatics.
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[1]
[1] 钟炳, 罗庆云. 甲醇在 HZSM-5上转化为烃类的催化反应机理[J]. 燃料化学学报, 1986, 14(1): 9-16. (ZHONG Bin, LUO Qing-yun. Reaction mechanism of methanol to hydrocarbons on HZSM-5[J]. Journal of Fuel Chemistry and Technology, 1986, 14(1): 9-16.)
-
[2]
[2] KOMATSU T, MESUDA M, YASHIMA T. Aromatization of butane on Pt–Ge intermetallic compounds supported on HZSM-5[J]. Appl Catal A, 2000, 194/195: 333-339.
-
[3]
[3] STÖCKER M. Methanol-to-hydrocarbons: Catalytic materials and their behavior[J]. Microporous Mesoporous Mater, 1999, 29(1/2): 3-48.
-
[4]
[4] KIM J, CHOI M, RYOO R. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process [J]. J Catal, 2010, 269(1): 219-228.
-
[5]
[5] CHEN J Q, BOZZANO A, GLOVER B, FUGLERUD T, KVISLE S. Recent advancements in ethylene and propylene production using the UOP/Hydro MTO process [J]. Catal Today, 2005, 106(1/4): 103-107.
-
[6]
[6] 赵仁殿, 金彰礼, 陶志华, 黄仲九. 芳烃工学[M]. 北京: 化学工业出版社,2001:1-11. (ZHAO Ren-dian, JIN Zhagn-li, TAO Zhi-hua, HUANG Zhong-jiu. Aromatic hydrocarbons processing technology[M]. Beijing: Chemical Industry Press, 2001: 1–11.)
-
[7]
[7] NI Y-M, SUN A-M, WU X-L, HAI G-L, HU J-L, LI T, LI G-X. The preparation of nano-sized HZSM-5 zeolite and its application in the aromatization of methanol[J]. Microporous Mesoporous Mater, 2011, 143(2/3): 435-442.
-
[8]
[8] LALIK E, LIU X, KLINOWSKI J. Role of gallium in the catalytic activity of zeolite -ZSM-5 for methanol conversion [J]. J Phys Chem, 1992, 96(2): 805-809.
-
[9]
[9] 田涛, 骞伟中, 孙玉建, 崔宇, 卢俨俨, 魏飞. Ag/ZSM- 5催化剂上甲醇芳构化过程[J]. 现代化工, 2009, 29(1): 55-58. (TIAN Tao, QIAN Wei-zhong, SUN Yu-jian, CUI Yu, LU Yan-yan, WEI Fei. Aromatization of methanol on Ag/ ZSM-5 catalyst[J]. Modern Chemical Industry, 2009, 29(1): 55-58.)
-
[10]
[10] 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.
-
[11]
[11] 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, 7(1/2): 1-8.
-
[12]
[12] CHOUDHARY T, KINAGE A, BANERJEE S, CHOUDHARY V. Influence of Si/Ga and Si/Al ratios on propane aromatization over highly active H-GaAlMFI[J]. Catal Commun, 2006, 7(3): 166-169.
-
[13]
[13] FRICKE R, KOSSLICK H, LISCHKE G, RICHTER M. Incorporation of gallium into zeolites: Syntheses, properties and catalytic application[J]. Chem Rev, 2000, 100(6): 2303-2405.
-
[14]
[14] 何红运, 孟宪平, 周凤岐, 庞文琴. 超微粉Ga-BETA沸石的水热合成及其结构研究[J]. 化学学报, 1994, 52(4): 380-385. (HE Hong-yun, MENG Xian-ping, ZHOU Fegn-qi, PANG Wen-qin. Synthesis and structural characterization of ultrafine powder Ga-BETA zeolite[J]. Acta Chimica Sinica, 1994, 52(4): 380-385.)
-
[15]
[15] 高志贤, 谭长瑜, 程昌瑞. 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): 301-306. (GAO Zhi-xian, TAN Chang-yu, CHENG Chang-rui. XPS study on state and distribution of gallium in Ga/HZSM-5 catalyst[J]. Journal of Fuel Chemistry and Technology 1995, 23(3): 301-306.)
-
[16]
[16] PARK J, KIM S B, HA J M, KIM M S, PARK H S, HAHM H S. Synthesis of the -MFI under atmospheric pressure[J]. Korean J Chem Eng, 2001, 18(4): 468-474.
-
[17]
[17] GNEP N S, DOYEMENT J Y, GUISNET M. Role of gallium species on the dehydrocyclodimerization of propane on ZSM5 catalysts[J]. J Mol Catal 1988, 45(3): 281-284.
-
[18]
[18] KHODAKOV A Y, KUSTOV L M, BONDARENKO T N, DERGACHEV A A, KAZANSKY V B, MINACHEV K M, BORBLY G, BEYER H K. Investigation of the different states of gallium in crystalline gallosilicates with pentasil structure and their role in propane aromatization[J]. Zeolites, 1990, 10(6): 603-607.
-
[19]
[19] CHOUDHARY V R, KINAGE A K, SIVADINARAYANA C, DEVADAS P, SANSARE S D, GUISNET M. H-gallosilicate(MFI) propane aromatization catalyst: Influence of Si/Ga ratio on acidity, activity and deactivation due to coking[J]. J Catal, 1996, 158(1): 34-50.
-
[20]
[20] 高志贤, 程昌瑞, 谭长瑜. Ga-Al-Si-ZSM-5的合成, 表征与催化性能[J]. 石油学报(石油加工) 1996, 12(1): 39-45. (GAO Zhi-xian, CHENG Chang-rui, TAN Chang-yu. Ga-A1-Si-ZSM-5 zeolites: Synthesis,characterization and catalytic properes[J]. Acta Petrolei Sinica(Petroleum Processing Section), 1996, 12(1): 39-45.)
-
[21]
[21] JOLY J F, AJOT H, MERLEN E, RAATZ F, ALARIO F. Parameters affecting the dispersion of the gallium phase of gallium H-MFI aromatization catalysts[J]. Appl Catal A, 1991, 79(2): 249-263.
-
[22]
[22] YAKERSON V I, VASINA T V, LAFER L I, SYTNYK V P, DYKH G L, MOKHOV A V, BRAGIN O V, MINACHEV K M. The properties of zinc and gallium containing pentasils - the catalysts for the aromatization of lower alkanes[J]. Catal Lett, 1989, 3(4): 339-345.
-
[23]
[23] SCURRELL M S. Prospects for the direct conversion of light alkanes to petrochemical feedstocks and liquid fuels: A review[J]. Appl Catal, 1987, 32:1-22.
-
[24]
[24] BAYENSE C R, VANHOOFF J H C. Aromatization of propane over gallium-containing H-ZSM-5 zeolites: Influence of the preparation method on the product selectivity and the catalytic stability[J]. Appl Catal, 1991, 79(1): 127-140.
-
[25]
[25] GUISNET M, GNEP N S. Mechanism of short-chain alkane transformation over protonic zeolites. Alkylation, disproportionation and aromatization[J]. Appl Catal A, 1996, 146(1): 33-64.
-
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