Citation: LIU Ya-cong, DONG Mei, FAN Wei-bin, QIN Zhang-feng, WANG Jian-guo. The deactivation mechanism of Zn/HZSM-5 zeolites in ethylene aromatization reaction[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(7): 826-834. shu

The deactivation mechanism of Zn/HZSM-5 zeolites in ethylene aromatization reaction

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: DONG Mei, mdong@sxicc.ac.cn FAN Wei-bin, fanwb@sxicc.ac.cn
Received Date: 27 March 2018
Revised Date: 4 May 2018

Fund Project: Strategic Priority Research Program of the Chinese Academy of Sciences XDA21000000The project was supported by the National Key R & D Program of China (2018YFB0604802), National Natural Science Foundation of China (21573270, U1510104, 21773281) and Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21000000)National Natural Science Foundation of China U1510104National Natural Science Foundation of China 21573270the National Key R & D Program of China 2018YFB0604802National Natural Science Foundation of China 21773281

Figures(9)

Zn/HZSM-5 zeolites, with zinc contents of 1%, 2%, and 3%, were prepared by impregnation method and characterized by XRD, N₂ adsorption, NH₃-TPD, Py-FTIR, XPS, and TG-DTA techniques to investigate the deactivation mechanism in ethylene aromatization reaction. It shows that coking is the main reason for catalysts deactivation, which is considerably depressed with the presence of Zn in the HZSM-5 catalysts. The deactivation is slow for the catalysts with low Zn loading. However, high content of Zn in the catalysts brings in problems such as decrease of surface area and microporous volume, and hence accelerates the deactivation. In the reaction, zinc species lose from the catalysts, accompanied with the migration and redistribution of Zn from bulk to surface of zeolite. The losing rate was constant with the time on stream, but influenced by the zinc content of the catalyst. ZnO on the external surface of the catalyst are the main species leaching from zeolite. Zn leaching is accelerated with the increase of zinc content, and has correlation with coking rate to some extent.
- Zn/HZSM-5 zeolite,
- ethylene aromatization,
- zinc content,
- Zn species,
- deactivation
1. [1]
  NAYAK V S, CHOUDHARY V R. Selective poisoning of stronger acid sites on HZSM-5 in the conversion of alcohols and olefins to aromatics[J]. Appl Catal, 1984,9(2):251-261. doi: 10.1016/0166-9834(84)80069-X
2. [2]
  KITAGAWA H, SENDODA Y, ONO Y. Transformation of propane into aromatic hydrocarbons over ZSM-5 zeolites[J]. J Catal, 1986,101(1):12-18. doi: 10.1016/0021-9517(86)90223-X
3. [3]
  ONO Y, KANAE K. Transformation of butanes over ZSM-5 zeolites. Part 1.-Mechanism of cracking of butanes over H-ZSM-5[J]. J Chem Soc Faraday Trans, 1991,87(4):663-667. doi: 10.1039/FT9918700663
4. [4]
  GUISNET M, GNEP N S, AITTALEB D, DOYEMET Y J. Conversion of light alkanes into aromatic hydrocarbons:VI. Aromatization of C_2-4 alkanes on H-ZSM-5-reaction mechanisms[J]. Appl Catal A:Gen, 1992,87(2):255-270. doi: 10.1016/0926-860X(92)80060-P
5. [5]
  BLEKEN F, SKISTAD W, BARBERA K, KUSTOVA M, BORDIGA S, BEATO P, LILLERUD K P, SVELLE S, OLSBYE U. Conversion of methanol over 10-ring zeolites with differing volumes at channel intersections:Comparison of TNU-9, IM-5, ZSM-11 and ZSM-5[J]. Phys Chem Chem Phys, 2011,13(7):2539-2549. doi: 10.1039/C0CP01982H
6. [6]
  ZHANG L, LIU S, XIE S, XU L. Organic template-free synthesis of ZSM-5/ZSM-11 co-crystalline zeolite[J]. Microporous Mesoporous Mater, 2012,147(1):117-126. doi: 10.1016/j.micromeso.2011.05.033
7. [7]
  MOLE T, ANDERSON J R, CREER G. The reaction of propane over ZSM-5-H and ZSM-5-Zn zeolite catalysts[J]. Appl Catal, 1985,17(1):141-154. doi: 10.1016/S0166-9834(00)82709-8
8. [8]
  CHEN X, DONG M, NIU X, WANG K, CHEN G, FAN W, WANG J, QIN Z. Influence of Zn species in HZSM-5 on ethylene aromatization[J]. Chin J Catal, 2015,36(6):880-888. doi: 10.1016/S1872-2067(14)60289-8
9. [9]
  NIU X, GAO J, WANG K, MIAO Q, DONG M, WANG G, FAN W, QIN Z, WANG J. Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics[J]. Fuel Process Technol, 2017,157:99-107. doi: 10.1016/j.fuproc.2016.12.006
10. [10]
  BISCARDI J A, MEITZNER G D, IGLESIA E. Structure and density of active Zn species in Zn/H-ZSM5 propane aromatization catalysts[J]. J Catal, 1998,179(1):192-202. doi: 10.1006/jcat.1998.2177
11. [11]
  BERNDT H, LIETZ G, LUCKE B, VOLTER J. Zinc promoted H-ZSM-5 catalysts for conversion of propane to aromatics I. Acidity and activity[J]. Appl Catal A:Gen, 1996,146(2):351-363. doi: 10.1016/S0926-860X(96)00092-0
12. [12]
  BERNDT H, LIETZ G, VOLTER 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. doi: 10.1016/S0926-860X(96)00124-X
13. [13]
  NIU X, GAO J, MIAO Q, DONG M, WANG G, FAN W, QIN Z, WANG J. Influence of preparation method on the performance of Zn-containing HZSM-5 catalysts in methanol-to-aromatics[J]. Microporous Mesoporous Mater, 2014,197:252-261. doi: 10.1016/j.micromeso.2014.06.027
14. [14]
  WEI Chun-lei, GAO Jie, WANG Kai, DONG Mei, FAN Wei-bin, QIN Zhang-feng, WANG Jian-guo. Effect of hydrogen pre-treatment on the catalytic properties of Zn/HZSM-5 zeolite for ethylene aromatization reaction[J]. Acta Phys Chim Sin, 2017,33(7):1483-1491. doi: 10.3866/PKU.WHXB201704133
15. [15]
  ROESSNER F, HAGEN A, MROCZEK U, KARGE H G, STEINBERG K H. Conversion of ethane into aromatic compounds on zsm-5 zeolites modified by zinc[J]. Stud Surf Sci Catal, 1993,75:1707-1710. doi: 10.1016/S0167-2991(08)64515-2
16. [16]
  CHENG Chang-rui, TAN Chang-yu, PENG Shao-yi. Study of lower paraffins to aromaticsⅡ. Conversion of light hydrocarbons over Zn/HZSM-5 catalysts[J]. J Fuel Chem Technol, 1995,23(3):289-294.
17. [17]
  ANUNZIATA O A, PIERELLA L B, MARINO R G. Selective transformation of light olefins into aromatic hydrocarbons over pentasil zeolites[J]. React Kinet Catal Lett, 1995,54(2):229-237. doi: 10.1007/BF02071013
18. [18]
  CHEN Jun, ZHANG Liu, KANG Hui-min. Stability of Zn promoter in Zn/HZSM-5 catalyst for C₃H₈ aromatization[J]. Chin J Catal, 2000,21(2):128-131.
19. [19]
  SHE Li-qin, WANG Duo-cai, LI Xuan-wen, LIU Xing-yun, HAN Ming. The states of zinc in ZnZSM-5 zeolites and their catalysis[J]. Acta Phys Chim Sin, 1994,10(3):247-253.
20. [20]
  CHEN Jun, ZHANG Liu, KANG Hui-min, DING Fu-xin. XPS characterization and propane aromatization over zinc promoted HZSM-5 catalysts[J]. Acta Pet Sin (Pet Process Sect), 2000,16(5):8-13.
1. [1]
  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
2. [2]
  Li Lin , Song-Lin Tian , Zhen-Yu Hu , Yu Zhang , Li-Min Chang , Jia-Jun Wang , Wan-Qiang Liu , Qing-Shuang Wang , Fang Wang . Molecular crowding electrolytes for stabilizing Zn metal anode in rechargeable aqueous batteries. Chinese Chemical Letters, 2024, 35(7): 109802-. doi: 10.1016/j.cclet.2024.109802
3. [3]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
4. [4]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
5. [5]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
6. [6]
  Xiping Dong , Xuan Wang , Zhixiu Lu , Qinhao Shi , Zhengyi Yang , Xuan Yu , Wuliang Feng , Xingli Zou , Yang Liu , Yufeng Zhao . Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability. Chinese Chemical Letters, 2024, 35(5): 108605-. doi: 10.1016/j.cclet.2023.108605
7. [7]
  Jie Zhou , Quanyu Li , Xiaomeng Hu , Weifeng Wei , Xiaobo Ji , Guichao Kuang , Liangjun Zhou , Libao Chen , Yuejiao Chen . Water molecules regulation for reversible Zn anode in aqueous zinc ion battery: Mini-review. Chinese Chemical Letters, 2024, 35(8): 109143-. doi: 10.1016/j.cclet.2023.109143
8. [8]
  Xinxiu Yan , Xizhe Huang , Yangyang Liu , Weishang Jia , Hualin Chen , Qi Yao , Tao Chen . Hyperbranched polyamidoamine protective layer with phosphate and carboxyl groups for dendrite-free Zn metal anodes. Chinese Chemical Letters, 2024, 35(10): 109426-. doi: 10.1016/j.cclet.2023.109426
9. [9]
  Yunfei Shen , Long Chen . Gradient imprinted Zn metal anodes assist dendrites-free at high current density/capacity. Chinese Journal of Structural Chemistry, 2024, 43(10): 100321-100321. doi: 10.1016/j.cjsc.2024.100321
10. [10]
  Qiaojia GUO , Junkai CAI , Chunying DUAN . Effects of anions on the structural regulation of Zn-salen-modified metal-organic cage. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2203-2211. doi: 10.11862/CJIC.20240209
11. [11]
  Yan-Kai Zhang , Yong-Zheng Zhang , Chun-Xiao Jia , Fang Wang , Xiuling Zhang , Yuhang Wu , Zhongmin Liu , Hui Hu , Da-Shuai Zhang , Longlong Geng , Jing Xu , Hongliang Huang . A stable Zn-MOF with anthracene-based linker for Cr(VI) photocatalytic reduction under sunlight irradiation. Chinese Chemical Letters, 2024, 35(12): 109756-. doi: 10.1016/j.cclet.2024.109756
12. [12]
  Chuyuan Lin , Hui Lin , Lingxing Zeng . Optimization strategy for rechargeable Zn metal batteries over wide-pH aqueous electrolytes. Chinese Journal of Structural Chemistry, 2025, 44(1): 100407-100407. doi: 10.1016/j.cjsc.2024.100407
13. [13]
  Shilong Li , Ming Zhao , Yefei Xu , Zhanyi Liu , Mian Li , Qing Huang , Xiang Wu . Performance optimization of aqueous Zn/MnO₂ batteries through the synergistic effect of PVP intercalation and GO coating. Chinese Chemical Letters, 2025, 36(3): 110701-. doi: 10.1016/j.cclet.2024.110701
14. [14]
  Shuwen SUN , Gaofeng WANG . Design and synthesis of a Zn(Ⅱ)-based coordination polymer as a fluorescent probe for trace monitoring 2, 4, 6-trinitrophenol. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 753-760. doi: 10.11862/CJIC.20240399
15. [15]
  Lin Peng , Xincheng Liang , Zelong Sun , Xingfa Chen , Dexin Meng , Renshu Huang , Qian Liu , Huan Wen , Shibin Yin . Microenvironment regulation of anode-electrolyte interface enables highly stable Zn anodes. Chinese Journal of Structural Chemistry, 2025, 44(4): 100542-100542. doi: 10.1016/j.cjsc.2025.100542
16. [16]
  Zihao Wang , Jing Xue , Zhicui Song , Jianxiong Xing , Aijun Zhou , Jianmin Ma , Jingze Li . Li-Zn alloy patch for defect-free polymer interface film enables excellent protection effect towards stable Li metal anode. Chinese Chemical Letters, 2024, 35(10): 109489-. doi: 10.1016/j.cclet.2024.109489
17. [17]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
18. [18]
  Jing LIANG , Qian WANG , Junfeng BAI . Synthesis and structures of cdq-topological quaternary and (4, 4, 8)-c topological quinary Zn-MOFs with both oxalic acid and triazole ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2186-2192. doi: 10.11862/CJIC.20240177
19. [19]
  Yanfen PENG , Xinyue WANG , Tianbao LIU , Xiaoshuo WU , Yujing WEI . Syntheses and luminescence of four Cd(Ⅱ)/Zn(Ⅱ) complexes constructed by 1,3‐bis(4H‐1,2,4‐triazole)benzene. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1416-1426. doi: 10.11862/CJIC.20250018
20. [20]
  Sumiya Akter Dristy , Md Ahasan Habib , Shusen Lin , Mehedi Hasan Joni , Rutuja Mandavkar , Young-Uk Chung , Md Najibullah , Jihoon Lee . Exploring Zn doped NiBP microspheres as efficient and stable electrocatalyst for industrial-scale water splitting. Acta Physico-Chimica Sinica, 2025, 41(7): 100079-0. doi: 10.1016/j.actphy.2025.100079

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(1337)
HTML views(257)

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