Citation: JI Hong-qiang, ZHANG Qiang, CHEN Lu, SHAN Hong-hong. Study on the reaction performance of methanol to aromatics over Zn/HZSM-5 catalysts with alumina[J]. Journal of Fuel Chemistry and Technology, ;2014, 42(11): 1387-1393. shu

Study on the reaction performance of methanol to aromatics over Zn/HZSM-5 catalysts with alumina

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, China

Corresponding author: ZHANG Qiang,
Received Date: 11 May 2014
Available Online: 23 July 2014
Fund Project: 青岛民生科技计划(13-1-3-126-nsh). (13-1-3-126-nsh)

The present paper investigated the effect of Zn modified HZSM-5 catalysts on the reaction performance of methanol to aromatics with the presence of alumina. The catalysts were characterized by BET, XRD, Py-FTIR, NH₃-TPD, and H₂-TPR techniques, respectively. The experimental result demonstrated that the introduction of alumina produced mesopores in the HZSM-5 catalyst and strengthened the stability of Zn species on the surface of the catalyst. The introduction of Zn species broke the structure of HZSM-5 zeolite and changed the surface acidity of the catalyst. In addition, Zn species might contribute to the dehydrogenation reaction of MTA. Meanwhile, the subsequent aromatization process of olefins was impressed. Within the scope of this study, the maximum value of aromatic yield (C_6~11) reached 21.0% when the loading of Zn was 0.5%. The aromatization of methanol is at the control of coke on the catalyst. However, the regenerated catalyst exhibited a higher aromatic yield.
- methanol,
- alumina,
- Zn,
- MTA,
- loading
1. [1]
  [1] 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.)
2. [2]
  [2] FREEMAN D, WELLS RICHARD P K, HUTCHINGS G J. Methanol to hydrocarbons: Enhanced aromatic formation using a composite Ga₂O₃/H-ZSM-5 catalyst[J]. Chem Commun, 2001, (18): 1754-1755.
3. [3]
  [3] FREEMAN D, WELLS RICHARD P K, HUTCHINGS G J. Conversion of methanol to hydrocarbons over Ga₂O₃/H-ZSM-5 and Ga₂O₃/WO₃ catalysts[J]. J Catal, 2002, 205(2): 358-365.
4. [4]
  [4] GIUSEPPE M G. Transformation of LPG into aromatic hydrocarbon and hydrogen over zeolite catalysts[J]. Catal Rev: Sci Eng, 1994, 36(2): 271-304.
5. [5]
  [5] CHANG C D, SILVESTRIA J. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. J Catal, 1977, 47(2): 249-259.
6. [6]
  [6] 王金英, 李文怀, 胡津仙. ZnHZSM-5上甲醇芳构化反应的研究[J]. 燃料化学学报, 2009, 37(5): 607-612.(WANG Jin-ying, LI Wen-huai, HU Jin-xian. Study of methanol to aromatics on ZnHZSM-5 catalyst[J]. Journal of Fuel Chemistry and Technology, 2009, 37(5): 607-612.)
7. [7]
  [7] 周建宏, 赵云, 宋金富, 艾沙·努拉洪, 胡佳, 陈黎行, 郭洪臣. 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, 29(7): 665-670.(ZHOU Jian-hong, ZHAO Yun, SONG Jin-fu, AISHA·Nulaha, HU Jia, CHEN Li-xing, GUO Hong-chen. Aromatization of C₅-C₈ alkane mixture over modified nano-sized HZSM-5 zeolite catalysts[J]. Chinese Journal of Catalysis, 2008, 29(7): 665-670.)
8. [8]
  [8] WANG T, TANG X P, HUANG X F, QIAN W Z, CUI Y, HUI X Y, YANG W, WEI F. Conversion of methanol to aromatics in fluidized bed reactor[J]. Catal Today, 2014, 233: 8-13.
9. [9]
  [9] 张金贵, 骞伟中, 汤效平, 沈葵, 王彤, 黄晓凡, 魏飞. 甲醇芳构化中催化剂酸性对脱烷基、烷基化和异构化反应的影响[J]. 物理化学学报, 2013, 29(6): 1281-1288.(ZHANG Jin-gui, QIAN Wei-zhong, TANG Xiao-ping, SHEN Kui, WANG Tong, HUANG Xiao-fan, WEI Fei. Influence of catalysts acidity on dealkylation, isomerization and alkylation in MTA process[J]. Acta Physico-Chimica Sinica, 2013, 29(6): 1281-1288.)
10. [10]
  [10] BJØRGEN M, JOENSEN F, SPANGSBERG HOLM M, OLSBYE U, LILLERUD K P, SVELLE S. Methanol to gasoline over zeolite H-ZSM-5: Improved catalyst performance by treatment with NaOH[J]. Appl Catal A: Gen, 2008, 345(1): 43-50.
11. [11]
  [11] WACHS I E. Raman and IR studies of surface metal oxide species on oxide supports: supported metal oxide catalysts[J]. Catal Today, 1996, 27(3): 437-455.
12. [12]
  [12] 佘励勤, 王多才, 李宣文, 刘兴云, 韩明. 锌在ZnZSM-5沸石中的形态及其催化作用[J]. 物理化学学报, 1994, 10(3): 301-305.(SHE Li-qin, WANG Duo-cai, LI Xuan-wen, LIU Xing-yun, HAN Ming. The states of zinc in ZnZSM-5 and their catalysis[J]. Acta Physico-Chimica Sinica, 1994, 10(3): 301-305.)
13. [13]
  [13] 桂建舟, 张晓彤, 胡之德, 孙兆林. 正己烷在ZnNi/HZSM-5上芳构化反应的研究[J]. 兰州大学学报(自然科学版), 2003, 39(5): 61-65.(GUI Jian-zhou, ZHANG Xiao-tong, HU Zhi-de, SUN Zhao-lin. A study of n-hexane aromatization on the ZnNi/HZSM-5 catalyst[J]. Journal of Lanzhou University (Natural Sciences), 2003, 39(5): 61-65.)
14. [14]
  [14] MASALSKA A. Properties and activity of Al₂O₃+ZSM-5 supported Ni and NiRu catalysts in 1-Methylnaphthalene hydrogenation: Effect of Ni incorporation method and calcing procedure[J]. Catal Lett, 2009, 127(1/2): 158-166.
15. [15]
  [15] 张欣, 徐广通, 邹亢, 黄南贵. S Zorb吸附剂中锌铝尖晶石形成原因的研究[J]. 石油学报(石油加工), 2012, 28(2): 242-247.(ZHANG Xin, XU Guang-tong, ZOU Kang, HUANG Nan-gui. Formation mechanism of gahnite in S Zorb sorbents[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2012, 28(2): 242-247.)
16. [16]
  [16] 程谟杰, 杨亚书. ZnHZSM-5上脱氢环化芳构化过程的探讨[J]. 分子催化, 1996, 10(6): 418-422.(CHENG Mo-jie, YANG Ya-shu. Study on dehydrocyclization and aromaization process over ZnHZSM-5 catalyst[J]. Journal of Molecular Catalysis (China), 1996, 10(6): 418-422.)
17. [17]
  [17] BISCARDI J A, IGLESISA E. Reaction pathways and rate-determining steps in reactions of alkanes on H-ZSM-5 and Zn/H-ZSM-5 catalysts[J]. J Catal, 1999, 182(1): 117-128.
18. [18]
  [18] ONO Y, ADACHI H, SENODA Y. Selective conversion of methanol into aromatic hydrocarbons over zinc-exchanged ZSM-5 zeolites[J]. J Chem Soc Faraday Trans 1: Phys Chem Cond Phas, 1988, 84(4): 1091-1099.
19. [19]
  [19] BERNADT H, LIETZ G, VØELTER J. Zinc promoted H-ZSM-5 catalysts for conversion of propane to aromatics: II. Nature of the active sites and their activation[J]. Appl Catal A: Gen, 1996, 146(2): 365-379.
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沈阳化工大学材料科学与工程学院沈阳 110142