Citation: LI Jun-hua, WANG Li-na, ZHANG Dan, QIAN Jian-hua, LIU Lin, XING Jin-juan. Effect of ZSM-5 acid modification on aromatization performance of methanol[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(8): 957-963. shu

Effect of ZSM-5 acid modification on aromatization performance of methanol

LI Jun-hua ^1,2 ,
WANG Li-na ¹ ,
ZHANG Dan ^1,, ,
QIAN Jian-hua ¹ ,
LIU Lin ¹ ,
XING Jin-juan ¹

1.
School of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013, China
2.
School of Chemistry and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China

Corresponding author: ZHANG Dan, bestzhangdan@163.com
Received Date: 20 March 2019
Revised Date: 18 June 2019

Fund Project: The project was supported by National Natural Science Foundation of China(21606117), Liaoning Natural Science Foundation(2015020623, 201602380), Liaoning Innovation Team Project(2018-479-14, LT2015001)and Bohai University Doctoral Start-up Fund(0518bs016, 0518bs019)Liaoning Natural Science Foundation 201602380Liaoning Natural Science Foundation 2015020623Bohai University Doctoral Start-up Fund 0518bs019Bohai University Doctoral Start-up Fund 0518bs016Liaoning Innovation Team Project LT2015001National Natural Science Foundation of China 21606117Liaoning Innovation Team Project 2018-479-14

Figures(7)

ZSM-5 zeolites were modified with tartaric acid, oxalic acid and nitric acid. The physicochemical properties of ZSM-5 zeolites, such as crystal structure, acid content, surface area and pore volume, were characterized by XRD, SEM, NH₃-TPD, XRF, ²⁷Al MAS NMR, pyridine adsorption infrared spectroscopy and N₂ adsorption-desorption isotherms. The catalytic activity of ZSM-5 zeolites were investigated under the condition of reaction temperature 422 ℃ and methanol mass space velocity of 4.74 h^-1. The specific surface area, acidity, pore volume and catalytic performance of the catalyst are affected by acid modification. The acid-modified zeolites show good catalytic activity in methanol aromatization (MTA) reaction, and oxalic acid modified catalyst shows higher catalytic activity and selectivity. The yield of aromatic hydrocarbons and BTX reaches 57.40% and 39.40% for reaction time at 8 h, respectively.
- ZSM-5 zeolite,
- acid-modified,
- methanol aromatization
1. [1]
  LIU B, LU S W, LIU E Z, HU X Y, FAN J. Methanol aromatization over CrZn-modified HZSM-5 catalysts[J]. Korean J Chem Eng, 2018,35(4):867-874. doi: 10.1007/s11814-017-0345-1
2. [2]
  ZHANG G Q, BAI T, CHEN T F, FAN W T, ZHANG X. Conversion of methanol to light aromatics on Zn-modified nano-HZSM-5 zeolite catalysts[J]. Ind Eng Chem Res, 2014,53(39):14932-14940. doi: 10.1021/ie5021156
3. [3]
  BI Y, WANG Y L, CHEN X, YU Z X, XU L. Methanol aromatization over HZSM-5 catalysts modified with different zinc salts[J]. Chin J Catal, 2014,35(10):1740-1751. doi: 10.1016/S1872-2067(14)60145-5
4. [4]
  LI J H, CHAO H, TONG K, XIANG H, ZHU Z R, HU Z H. CO₂ atmosphere-enhanced methanol aromatization over the NiO-HZSM-5catalyst[J]. RSC Adv, 2014,4(84):44377-44385. doi: 10.1039/C4RA06572G
5. [5]
  WANG N, QIAN W Z, SHEN K, SU C, WEI F. Bayberry-like ZnO/MFI zeolite as high performance methanol-to-aromatics catalyst[J]. Chem Commun, 2016,52(10):2011-2014. doi: 10.1039/C5CC08471G
6. [6]
  ZAIDI H K, PANT K K. Catalytic conversion of mathanol to gasoline rang hydrocarbons[J]. Catal Today, 2004,96(3):155-160. doi: 10.1016/j.cattod.2004.06.123
7. [7]
  ZHANG Jin-gui, QIAN Wei-zhong, TANG Xiao-ping, SHEN Kui, WANG Tong, HUANG Xiao-fan, WEI Fei. Influence of catalyst acidity on dealkylation, isomerization and alkylation in MTA process[J]. Acta Phys-Chim Sin, 2013,29(6):1281-1288. doi: 10.3866/PKU.WHXB201304101
8. [8]
  DUAN Chao, QI Xiao-feng, ZHANG Rui, WANG Hong-mei, XIE Xiao-li, PAN Rui-juan. Methanol aromatization over ZSM-5 catalysts prepared with different oxides[J]. Ind Catal, 2014,22(6):437-442. doi: 10.3969/j.issn.1008-1143.2014.06.006
9. [9]
  GENG Rui, DONG Mei, WANG Hao, NIU Xian-jun, FAN Wei-bin, WANG Jian-guo, QIN Zhang-feng. An investigation on the catalytic performance of 10 MR zeolites in methanol aromatization reaction[J]. J Fuel Chem Technol, 2014,42(9):1119-1127. doi: 10.3969/j.issn.0253-2409.2014.09.013
10. [10]
  SHEN X Q, KANG J C, NIU W, WANG M G, ZHANG Q H, WANG Y. Impact of hierarchical pore structure on catalytic performances of MFI zeolites modified by ZnO for the conversion of methanol to aromatics[J]. Catal Sci Technol, 2017,7(16):3598-3612. doi: 10.1039/C7CY01041A
11. [11]
  WANG Xiao-xing, ZHANG Tao, ZHANG Jun-feng, XIE Hong-jian, HAN Yi-zhuo, TAN Yi-sheng. Synthesis of mesoporous HZnZSM-5 zeolite and its catalytic performance in methanol aromatization[J]. Acta Pet Sin (Pet Process Sect), 2014,30(2):336-342. doi: 10.3969/j.issn.1001-8719.2014.02.022
12. [12]
  BARBER K, BONINO F, BORDIGA S, JANSSENS T V W, BEATO P. Structure-deactivation relationship for ZSM-5 catalysts governed by framework defects[J]. J Catal, 2011,280(2):196-205. doi: 10.1016/j.jcat.2011.03.016
13. [13]
  WANG Lu, XU Li-xing, LI Jian, REN Hao-nan, CHU Shuang, WANG Li-juan, YANG Li-na. Studies on micro-bimodal mesoporous core-shell HZSM-5@BMMs catalyst for methanol to aromatics[J]. Fine Chem, 2018,35(9):1562-1566.
14. [14]
  WANG P F, HUANG L Z, LI J F, DONG M, WANG J G, TATSUMI T, FAN W B. Catalytic properties and deactivation behavior of H-MCM-22 in the conversion of methanol tohydrocarbons[J]. RSC Adv, 2015,5(36):28794-28802. doi: 10.1039/C5RA00048C
15. [15]
  MENG F J, WANG Y Q, WANG S H. Methanol to gasoline over zeolite ZSM-5:Improved catalyst performance by treatment with HF[J]. RSC Adv, 2016,6(63):58586-58593. doi: 10.1039/C6RA14513B
16. [16]
  ZHOU J, TENG J W, REN L P, WANG Y D, LIU Z C, LIU W, YANG W M, XIE Z K. Full-crystalline hierarchical monolithic ZSM-5 zeolites as superiorly active and long-lived practical catalysts in methanol-to-hydrocarbons reaction[J]. J Catal, 2016,340:166-176. doi: 10.1016/j.jcat.2016.05.009
17. [17]
  YOU S J, PARK E D. Effects of dealumination and desilication of H-ZSM-5 on xylose dehydration[J]. Microporous Mesoporous Mater, 2014,186:121-129. doi: 10.1016/j.micromeso.2013.11.042
18. [18]
  ZHOU F, GAO Y, WU G, MA F W, LIU C T. Improved catalytic performance and decreased coke formation in post-treated ZSM-5 zeolites for methanol aromatization[J]. Microporous Mesoporous Mater, 2017,240:96-107. doi: 10.1016/j.micromeso.2016.11.014
19. [19]
  FENG R, YAN X L, HU X Y, WANG Y L, LI Z, HOU K, LIU J W. Hierarchical ZSM-5 zeolite designed by combining desilication and dealumination with related study of n-heptane cracking performance[J]. J Porous Mater, 2018,25(6):1743-1756. doi: 10.1007/s10934-018-0587-2
20. [20]
  SKLENAK S, DEDECEK J, LI C B, WICHTERLOVA B, GABOVA V, SIERKA M, SAUER T. Aluminium siting in the ZSM-5 framework by combination of high resolution 27Al NMR and DFT/MM calculations[J]. Phys Chem Chem Phys, 2009,11(8):1237-1247. doi: 10.1039/B807755J
21. [21]
  WU Tao, YUAN Gui-mei, CHEN Sheng-li, XUE Yang, LI Shu-juan. Synthesis of ZSM-5 and its application in butylene catalytic cracking[J]. J Fuel Chem Technol, 2017,45(2):182-188. doi: 10.3969/j.issn.0253-2409.2017.02.007
22. [22]
  TOPSØE N Y, PEDERSEN K, DEROUAN E G. Infrared and temperature-programmed desorption study of the acidic properties of ZSM-5-type zeolites[J]. J Catal, 1981,70:41-52. doi: 10.1016/0021-9517(81)90315-8
23. [23]
  CHEN Xiao-di, LI Xue-gang, LI Hu, ZHANG Yu-ling, HAN Jia-ji, XIAO Wen-de. Organic acid-modified high silica HZSM-5 zeolite and application thereof in methanol to propylene[J]. Petrochem Technol, 2018,47(5):408-414. doi: 10.3969/j.issn.1000-8144.2018.05.002
24. [24]
  WEI Z H, XIA T F, LIU M H, CAO Q S, XU Y R, ZHU K, ZHU X D. Alkaline modification of ZSM-5 catalysts for methanol aromatization:The effect of the alkaline concentration[J]. Front Chem Sci Eng, 2015,9(4):450-460. doi: 10.1007/s11705-015-1542-2
25. [25]
  JIA Y M, WANG J W, ZHANG K, LIU S B, CHEN G L, YANG Y F, DING C M, LIU P. Catalytic conversion of methanol to aromatics over nanosized HZSM-5 zeolite modified by ZnSiF₆·6H₂O[J]. Catal Sci Technol, 2017,7(8):1776-1791. doi: 10.1039/C7CY00143F
26. [26]
  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 H[J]. Microporous Mesoporous Mater, 2011,143(2/3):435-442.
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]
  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
3. [3]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  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-. doi: 10.3866/PKU.WHXB202406012
9. [9]
  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
10. [10]
  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
11. [11]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
12. [12]
  Wenjun Yang , Qiaoling Tan , Wenjiao Xie , Xiaoyu Pan , Youyong Yuan . Construction and Characterization of Calcium Alginate Microparticle Drug Delivery System: A Novel Design and Teaching Practice in Polymer Experiments. University Chemistry, 2025, 40(3): 371-380. doi: 10.12461/PKU.DXHX202405150
13. [13]
  Xiaosong PU , Hangkai WU , Taohong LI , Huijuan LI , Shouqing LIU , Yuanbo HUANG , Xuemei LI . Adsorption performance and removal mechanism of Cd(Ⅱ) in water by magnesium modified carbon foam. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1537-1548. doi: 10.11862/CJIC.20240030
14. [14]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
15. [15]
  Qingying Gao , Tao Luo , Jianyuan Su , Chaofan Yu , Jiazhu Li , Bingfei Yan , Wenzuo Li , Zhen Zhang , Yi Liu . Refinement and Expansion of the Classic Cinnamic Acid Synthesis Experiment. University Chemistry, 2024, 39(5): 243-250. doi: 10.3866/PKU.DXHX202311074
16. [16]
  Limei CHEN , Mengfei ZHAO , Lin CHEN , Ding LI , Wei LI , Weiye HAN , Hongbin WANG . Preparation and performance of paraffin/alkali modified diatomite/expanded graphite composite phase change thermal storage material. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 533-543. doi: 10.11862/CJIC.20230312
17. [17]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
18. [18]
  Xiaotian ZHU , Fangding HUANG , Wenchang ZHU , Jianqing ZHAO . Layered oxide cathode for sodium-ion batteries: Surface and interface modification and suppressed gas generation effect. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 254-266. doi: 10.11862/CJIC.20240260
19. [19]
  Yingtong Shi , Guotong Xu , Guizeng Liang , Di Lan , Siyuan Zhang , Yanru Wang , Daohao Li , Guanglei Wu . PEG-VN改性PP隔膜用于高稳定性高效率锂硫电池. Acta Physico-Chimica Sinica, 2025, 41(7): 100082-. doi: 10.1016/j.actphy.2025.100082
20. [20]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(1683)
HTML views(281)

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