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(8): 961-969. shu

Aromatization of propane over Ga-modified ZSM-5 catalysts

1.
1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;

Corresponding author: ZHU Hua-qing, WANG Jian-guo,
Received Date: 31 March 2015
Available Online: 12 May 2015
Fund Project: 国家自然科学基金(21273264) (21273264)国家重点基础研究发展规划(973计划,2011CB201403,2011CB201406)。 (973计划,2011CB201403,2011CB201406)

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.
- propane aromatization,
- Si/Al mol ratio,
- gallium species,
- ZSM-5 molecular sieves,
- pretreatment
1. [1]
  [1] ONO Y. Transformation of lower alkanes into aromatic hydrocarbons over ZSM-5 zeolites[J]. Catal Rev: Sci Eng, 1992, 34(3): 179-226.
2. [2]
  [2] 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.
3. [3]
  [3] 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.
4. [4]
  [4] 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.
5. [5]
  [5] 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.
6. [6]
  [6] GUISNET M, GNEP N S. Aromatization of short chain alkanes on zeolite catalysts[J]. Appl Catal A: Gen, 1992, 89(1): 1-30.
7. [7]
  [7] 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.
8. [8]
  [8] 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.
9. [9]
  [9] 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.)
10. [10]
  [10] 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.
11. [11]
  [11] 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.
12. [12]
  [12] 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.
13. [13]
  [13] 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.)
14. [14]
  [14] 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.
15. [15]
  [15] HAAG W O, LAGO R M, WEISZ P B. The active-site of acidic aluminosilicate catalysts[J]. Nature, 1984, 309(5969): 589-591.
16. [16]
  [16] 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.
17. [17]
  [17] 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.
18. [18]
  [18] 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.)
19. [19]
  [19] 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.
20. [20]
  [20] 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.)
21. [21]
  [21] 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.
22. [22]
  [22] 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.
23. [23]
  [23] AUSAVASUKHI A, SOOKNOI T. Tunable activity of HZSM-5 with H₂ treatment: Ethane dehydrogenation[J]. Catal Comm, 2014, 45(1): 63-68.
1. [1]
  Yi RU , Tao MENG , Zhaoteng XUE , Dongsen MAO . Synergistic catalysis of Al distribution and pore structure in ZSM-5 zeolite for bioethanol-to-propylene. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 247-262. doi: 10.11862/CJIC.20250255
2. [2]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
3. [3]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-0. doi: 10.3866/PKU.WHXB202406012
4. [4]
  Qinhui Guan , Yuhao Guo , Na Li , Jing Li , Tingjiang Yan . Molecular sieve-mediated indium oxide catalysts for enhancing photocatalytic CO₂ hydrogenation. Acta Physico-Chimica Sinica, 2025, 41(11): 100133-0. doi: 10.1016/j.actphy.2025.100133
5. [5]
  Huaihao CHEN , Lingwen ZHANG , Yukun CHEN , Jianjun ZHANG . A water-stable metal-organic framework probe for Al³⁺/Ga³⁺/In³⁺ detection. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2601-2608. doi: 10.11862/CJIC.20250184
6. [6]
  Xiaorui Chen , Xuan Luo , Tongming Su , Xinling Xie , Liuyun Chen , Yuejing Bin , Zuzeng Qin , Hongbing Ji . Ga-doped Cu/γ-Al₂O₃ bifunctional interface sites promote the direct hydrogenation of CO₂ to DME. Acta Physico-Chimica Sinica, 2025, 41(10): 100126-0. doi: 10.1016/j.actphy.2025.100126
7. [7]
  Xinyu You , Xin Zhang , Shican Jiang , Yiru Ye , Lin Gu , Hexun Zhou , Pandong Ma , Jamal Ftouni , Abhishek Dutta Chowdhury . Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process. Chinese Journal of Structural Chemistry, 2024, 43(4): 100265-100265. doi: 10.1016/j.cjsc.2024.100265
8. [8]
  Tangsheng Guan , Ruizhi Yang , Pingyue Geng , Yuhong Lin , Shui Hu , Xiaojuan Chen , Houjin Li , Yong Shen . Innovative Digital Experiments for Glutathione-Targeted Anticancer Drugs in Redox Systems. University Chemistry, 2026, 41(1): 144-158. doi: 10.12461/PKU.DXHX202505028
9. [9]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
10. [10]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
11. [11]
  Shanyuan Bi , Jin Zhang , Dengchao Peng , Danhong Cheng , Jianping Zhang , Lupeng Han , Dengsong Zhang . Improved N₂ selectivity for low-temperature NO_x reduction over etched ZSM-5 supported MnCe oxide catalysts. Chinese Chemical Letters, 2025, 36(5): 110295-. doi: 10.1016/j.cclet.2024.110295
12. [12]
  Zhuwei Yang , Linsen Li , Yijie Lin , Xinyuan Tao , Xiao Liu , Lei Chen , Ming Ma , Li Lin , Riguang Zhang , Jiayuan Li , Zhao Jiang . Regulating the Oxygen Vacancies in Ni-CexZr1-xO2/ZSM-5 to Improve the Long-term Stability for Methane Dry Reforming. Chinese Journal of Structural Chemistry, 2025, 44(8): 100632-100632. doi: 10.1016/j.cjsc.2025.100632
13. [13]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
14. [14]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
15. [15]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
16. [16]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
17. [17]
  Liangliang Song , Haoyan Liang , Shunqing Li , Bao Qiu , Zhaoping Liu . Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries. Acta Physico-Chimica Sinica, 2025, 41(8): 100085-0. doi: 10.1016/j.actphy.2025.100085
18. [18]
  Mingjie Lei , Wenting Hu , Kexin Lin , Xiujuan Sun , Haoshen Zhang , Ye Qian , Tongyue Kang , Xiulin Wu , Hailong Liao , Yuan Pan , Yuwei Zhang , Diye Wei , Ping Gao . Accelerating the reconstruction of NiSe₂ by Co/Mn/Mo doping for enhanced urea electrolysis. Acta Physico-Chimica Sinica, 2025, 41(8): 100083-0. doi: 10.1016/j.actphy.2025.100083
19. [19]
  Aoyun Meng , Zhenhua Li , Guoyuan Xiong , Zhen Li , Jinfeng Zhang . S-scheme heterojunction Al₆Si₂O₁₃/BiOBr with enhanced charge transfer effect for efficient and stable photocatalytic degradation of triazophos and dichlorvos pesticides. Acta Physico-Chimica Sinica, 2026, 42(5): 100186-0. doi: 10.1016/j.actphy.2025.100186
20. [20]
  Rui Gao , Ying Zhou , Yifan Hu , Siyuan Chen , Shouhong Xu , Qianfu Luo , Wenqing Zhang . Design, Synthesis and Performance Experiment of Novel Photoswitchable Hybrid Tetraarylethenes. University Chemistry, 2024, 39(5): 125-133. doi: 10.3866/PKU.DXHX202310050

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(710)
HTML views(33)

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