Citation: YE Yu-ling, FU Meng-qian, CHEN Hong-lin, ZHANG Xiao-ming. Effect of acidity on the catalytic performance of ZSM-5 zeolites in the synthesis of trioxane from formaldehyde[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(3): 311-320. shu

Effect of acidity on the catalytic performance of ZSM-5 zeolites in the synthesis of trioxane from formaldehyde

1.
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
2.
College of Chemical Engineering, Sichuan University of Science & Engineering, Zigong 643000, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: CHEN Hong-lin, hlchen@cioc.ac.cn
Received Date: 20 January 2020
Revised Date: 9 March 2020

Fund Project: The project was supported by the National Key R & D Program of China (2018YFB0604902)The project was supported by the National Key R & D Program of China 2018YFB0604902

Figures(10)

ZSM-5 zeolite is considered as an effective catalyst in the synthesis of trioxane from formaldehyde. In this work, a series of ZSM-5 zeolites with different SiO₂/Al₂O₃ molar ratios were used in the synthesis of trioxane from formaldehyde; through characterization by XRF, XRD, SEM, NH₃-TPD, Py-FTIR and ²⁷Al MAS NMR, the effect of acidity including the Brønsted and Lewis acid sites on the catalytic performance of ZSM-5 zeolites in the trioxane synthesis was investigated. The results indicate that the ZSM-5-250 zeolite with a SiO₂/Al₂O₃ molar ratio of 250 exhibits excellent catalytic performance in the synthesis of trioxane. The ZSM-5-250 zeolite owns sufficient amount of Brønsted acid sites which are active for the synthesis of formaldehyde to trioxane; meanwhile, it has few Lewis acid sites and can then effectively inhibit various side-reactions like the Cannizzaro or Tishchenko reactions. Moreover, the ZSM-5-250 zeolite displays high stability with a single-pass lifetime of 114 h and can be regenerated easily through calcination at 550℃.
- trioxane,
- ZSM-5 zeolite,
- formaldehyde,
- acidity,
- Brønsted acid,
- Lewis acid
1. [1]
  MU Y B, JIA M C, JIANG W, WAN X B. A novel branched polyoxymethylene synthesized by cationic copolymerization of 1, 3, 5-Trioxane with 3-(Alkoxymethyl)-3-ethyloxetane[J]. Macromol Chem Phys, 2013,214(23):2752-2760. doi: 10.1002/macp.201300473
2. [2]
  HOFFMANN M, BIZZARRI C, LEITNER W, MULLER T E. Reaction pathways at the initial steps of trioxane polymerisation[J]. Catal Sci Technol, 2018,8(21):5594-5603. doi: 10.1039/C8CY01691G
3. [3]
  WU Q, LI W, WANG M, HAO Y, CHU T, SHANG J, LI H, ZHAO Y, JIAO Q. Synthesis of polyoxymethylene dimethyl ethers from methylal and trioxane catalyzed by bronsted acid ionic liquids with different alkyl groups[J]. Rsc Adv, 2015,5(71):57968-57974. doi: 10.1039/C5RA08360E
4. [4]
  BARANOWSKI C J, BAHMANPOUR A M, KROCHER O. Catalytic synthesis of polyoxymethylene dimethyl ethers (OME):A review[J]. Appl Catal B:Environ, 2017,217:407-420. doi: 10.1016/j.apcatb.2017.06.007
5. [5]
  ROESSLER D G-U S-S V. Procédé de préparation du trioxanne: FR1374872[P]. 1964-10-09.
6. [6]
  BALASHOV A L, KRASNOV V L, DANOV S M, CHERNOV A Y, SULIMOV A V. Formation of cyclic oligomers in concentrated aqueous solutions of formaldehyde[J]. J Struct Chem, 2001,42(3):398-403. doi: 10.1023/A:1012408904389
7. [7]
  GRUTZNER T, HASSE H. Solubility of formaldehyde and trioxane in aqueous solutions[J]. J Chem Eng Data, 2004,49(3):642-646. doi: 10.1021/je030243h
8. [8]
  MAIWALD M, GRUTZNER T, STROFER E, HASSE H. Quantitative NMR spectroscopy of complex technical mixtures using a virtual reference:Chemical equilibria and reaction kinetics of formaldehyde-water-1, 3, 5-trioxane[J]. Anal Bioanal Chem, 2006,385(5):910-917. doi: 10.1007/s00216-006-0477-3
9. [9]
  GRUTZNER T, HASSE H, LANG N, SIEGERT M, STROFER E. Development of a new industrial process for trioxane production[J]. Chem Eng Sci, 2007,62(18/20):5613-5620.
10. [10]
  MASAMOTO J, HAMANAKA K, YOSHIDA K, NAGAHARA H, KAGAWA K, IWAISAKO T, KOMAKI H. Synthesis of trioxane using heteropolyacids as catalyst[J]. Angew Chem-Int Ed, 2000,39(12):2102-2104. doi: 10.1002/1521-3773(20000616)39:12<2102::AID-ANIE2102>3.0.CO;2-E
11. [11]
  XIA C, TANG Z, CHEN J, ZHANG X, LI Z, GUO E. Method of synthesizing trioxymethylene from formaldehyde by the catalytic action of an ionic liquid: US7244854B2[P]. 2007-07-17.
12. [12]
  ZHAO Y M, HU Y F, QI J G, MA W T. Bronsted-acidic ionic liquids as catalysts for synthesizing trioxane[J]. Chin J Chem Eng, 2016,24(10):1392-1398. doi: 10.1016/j.cjche.2016.05.001
13. [13]
  ARIAS-UGARTE R, WEKESA F S, FINDLATER M. Selective aldol condensation or cyclotrimerization reactions catalyzed by FeCl₃[J]. Tetrahedron Lett, 2015,56(19):2406-2411. doi: 10.1016/j.tetlet.2015.03.040
14. [14]
  KIEDIK M, KRUEGER A. Synthesis of trioxane in presence of sulfuric acid and ion-exchange resins as catalyst-comparisons of methods[J]. Przem Chem, 1990,69(12):539-540.
15. [15]
  DINTZNER M R, MONDJINOU Y A, PILEGGI D J. Montmorillonite clay-catalyzed cyclotrimerization and oxidation of aliphatic aldehydes[J]. Tetrahedron Lett, 2010,51(5):826-827. doi: 10.1016/j.tetlet.2009.12.009
16. [16]
  LEE S O, KITCHIN S J, HARRIS K D M, SANKAR G, DUGAL M, THOMAS J M. Acid-catalyzed trimerization of acetaldehyde:A highly selective and reversible transformation at ambient temperature in a zeolitic solid[J]. J Phys Chem B, 2002,106(6):1322-1326. doi: 10.1021/jp012440y
17. [17]
  MORI H, YAMAZAKI T, OZAWA S, OGINO Y. Liquid-phase reaction of acetaldehyde over various ZSM-5 zeolites[J]. Bull Chem Soc Jpn, 1993,66(9):2498-2504. doi: 10.1246/bcsj.66.2498
18. [18]
  YE Y, YAO M, CHEN H X Z. Influence of silanol defects of ZSM-5 zeolites on trioxane synthesis from formaldehyde[J]. Catal Lett, 2020,150(5):1445-1453. doi: 10.1007/s10562-019-03040-x
19. [19]
  ISHIDA H, AKAGISHI K. The synthetic reaction of trioxane from formalin on the zeolite catalysts[J]. Nippon Kagaku Kaishi, 1996(3):290-297. doi: 10.1246/nikkashi.1996.290
20. [20]
  FU M, YE Y, LEI Q, CHEN H, ZHANG X. Research on the synthetic 1, 3, 5-trioxane over ZSM-5 zeolite[J]. Chin J Synthetic Chem, 2020.
21. [21]
  RODRIGUEZ-GONZALEZ L, SIMON U. NH₃-TPD measurements using a zeolite-based sensor[J]. Meas Sci Technol, 2010,21(2)7.
22. [22]
  DIEZ V K, APESTEGUIA C R, DI COSIMO J I. Synthesis of ionones on solid Bronsted acid catalysts:Effect of acid site strength on ionone isomer selectivity[J]. Catal Today, 2010,149(3/4):267-274.
23. [23]
  WU W Q, WEITZ E. Modification of acid sites in ZSM-5 by ion-exchange:An in-situ FT-IR study[J]. Appl Surf Sci, 2014,316:405-415. doi: 10.1016/j.apsusc.2014.07.194
24. [24]
  JIN F, LI Y D. A FT-IR and TPD examination of the distributive properties of acid sites on ZSM-5 zeolite with pyridine as a probe molecule[J]. Catal Today, 2009,145(1/2):101-107.
25. [25]
  ISERNIA L F. FT-IR study of the relation, between extra-framework aluminum species and the adsorbed molecular water, and its effect on the acidity in ZSM-5 steamed zeolite[J]. Mater Res-Ibero-Am J, 2013,16(4):792-802.
26. [26]
  RODRIGUEZ-GONZALEZ L, HERMES F, BERTMER M, RODRIGUEZ-CASTELLON E, JIMENEZ-LOPEZ A, SIMON U. The acid properties of H-ZSM-5 as studied by NH₃-TPD and ²⁷Al-MAS-NMR spectroscopy[J]. Appl Catal A:Gen, 2007,328(2):174-182. doi: 10.1016/j.apcata.2007.06.003
27. [27]
  WOOLERY G L, KUEHL G H, TIMKEN H C, CHESTER A W, VARTULI J C. On the nature of framework bronsted and lewis acid sites in ZSM-5[J]. Zeolites, 1997,19(4):288-296. doi: 10.1016/S0144-2449(97)00086-9
28. [28]
  LI S H, HUANG S J, SHEN W L, ZHANG H L, FANG H J, ZHENG A M, LIU S B, DENG F. Probing the spatial proximities among acid sites in dealuminated H-Y zeolite by solid-state NMR spectroscopy[J]. J Phys Chem C, 2008,112(37):14486-14494. doi: 10.1021/jp803494n
29. [29]
  GELBARD G. Organic synthesis by catalysis with ion-exchange resins[J]. Ind Eng Chem Res, 2005,44(23):8468-8498. doi: 10.1021/ie0580405
30. [30]
  BIRDJA Y Y, KOPER M T M. The importance of cannizzaro-type reactions during electrocatalytic reduction of carbon dioxide[J]. J Am Chem Soc, 2017,139(5):2030-2034. doi: 10.1021/jacs.6b12008
31. [31]
  RUSSELL A E, MILLER S P, MORKEN J P. Efficient Lewis acid catalyzed intramolecular cannizzaro reaction[J]. J Org Chem, 2000,65(24):8381-8383. doi: 10.1021/jo0010734
32. [32]
  OESTREICH D, LAUTENSCHUTZ L, ARNOLD U, SAUER J. Reaction kinetics and equilibrium parameters for the production of oxymethylene dimethyl ethers (OME) from methanol and formaldehyde[J]. Chem Eng Sci, 2017,163:92-104. doi: 10.1016/j.ces.2016.12.037
33. [33]
  INDU B, ERNST W R, GELBAUM L T. Methanol formic acid esterfication equilibrium in sulfuric acid solutions-influence of sodium salts[J]. Ind Eng Chem Res, 1993,32(5):981-985. doi: 10.1021/ie00017a031
34. [34]
  MORRIS S A, GUSEV D G. Rethinking the claisen-tishchenko reaction[J]. Angew Chem-Int Ed, 2017,56(22):6228-6231. doi: 10.1002/anie.201611186
35. [35]
  WU J B, ZHU H Q, WU Z W, QIN Z F, YAN L, DU B L, FAN W B, WANG J G. High Si/Al ratio HZSM-5 zeolite:An efficient catalyst for the synthesis of polyoxymethylene dimethyl ethers from dimethoxymethane and trioxymethylene[J]. Green Chem, 2015,17(4):2353-2357. doi: 10.1039/C4GC02510E
36. [36]
  ARROYO S T, GARCIA A H, ALVERO M M, MARTIN J A S. Theoretical study of the neutral hydrolysis of methyl formate via a concerted and stepwise water-assisted mechanism using free-energy curves and molecular dynamics simulation[J]. Struct Chem, 2011,22(4):909-915. doi: 10.1007/s11224-011-9777-0
37. [37]
  GLARBORG P, ALZUETA M U, KJAERGAARD K, DAM-JOHANSEN K. Oxidation of formaldehyde and its interaction with nitric oxide in a flow reactor[J]. Combust Flame, 2003,132(4):629-638. doi: 10.1016/S0010-2180(02)00535-7
38. [38]
  HOCHGREB S, DRYER F L. A comprehensive study on CH₂O oxidation kinetics[J]. Combust Flame, 1992,91(3/4):257-284.
39. [39]
  OLM C, VARGA T, VALKO E, CURRAN H J, TURANYI T. Uncertainty quantification of a newly optimized methanol and formaldehyde combustion mechanism[J]. Combust Flame, 2017,186:45-64. doi: 10.1016/j.combustflame.2017.07.029
1. [1]
  Zhenhao Wang , Yuliang Tang , Ruyu Li , Shuai Tian , Yu Tang , Dehai Li . Bioinspired synthesis of cochlearol B and ganocin A. Chinese Chemical Letters, 2024, 35(7): 109247-. doi: 10.1016/j.cclet.2023.109247
2. [2]
  Jiajun Lu , Zhehui Liao , Tongxiang Cao , Shifa Zhu . Synergistic Brønsted/Lewis acid catalyzed atroposelective synthesis of aryl-β-naphthol. Chinese Chemical Letters, 2025, 36(1): 109842-. doi: 10.1016/j.cclet.2024.109842
3. [3]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
4. [4]
  Ruofan Qi , Jing Zhang , Wang Sun , Bai Yu , Zhenhua Wang , Kening Sun . Solid-acid-Lewis-base interaction accelerates lithium ion transport for uniform lithium deposition. Chinese Chemical Letters, 2025, 36(6): 110009-. doi: 10.1016/j.cclet.2024.110009
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  Jie Ma , Jianxiang Wang , Jianhua Yuan , Xiao Liu , Yun Yang , Fei Yu . The regulating strategy of hierarchical structure and acidity in zeolites and application of gas adsorption: A review. Chinese Chemical Letters, 2024, 35(11): 109693-. doi: 10.1016/j.cclet.2024.109693
9. [9]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
10. [10]
  Qing Li , Yumei Feng , Yuhua Xie , Qi Xu , Yifei Li , Yingjie Yu , Fang Luo , Zehui Yang . MOF derived RuO₂/V₂O₅ nanoneedles for robust and stable water oxidation in acid. Chinese Chemical Letters, 2025, 36(7): 111074-. doi: 10.1016/j.cclet.2025.111074
11. [11]
  Quanxing Mao , Zhengliang Wang , Zhinan Hu , Ziqi Yang , Hui Li , Yali Yao , Zijun Yong , Tianyi Ma . Facial detection of formaldehyde by using acidichromic carbon dots and the reaction between formaldehyde and ammonium chloride. Chinese Chemical Letters, 2025, 36(7): 110499-. doi: 10.1016/j.cclet.2024.110499
12. [12]
  Zhenghua ZHAO , Qin ZHANG , Yufeng LIU , Zifa SHI , Jinzhong GU . Syntheses, crystal structures, catalytic and anti-wear properties of nickel(Ⅱ) and zinc(Ⅱ) coordination polymers based on 5-(2-carboxyphenyl)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 621-628. doi: 10.11862/CJIC.20230342
13. [13]
  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
14. [14]
  Weizhong LING , Xiangyun CHEN , Wenjing LIU , Yingkai HUANG , Yu LI . Syntheses, crystal structures, and catalytic properties of three zinc(Ⅱ), cobalt(Ⅱ) and nickel(Ⅱ) coordination polymers constructed from 5-(4-carboxyphenoxy)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1803-1810. doi: 10.11862/CJIC.20240068
15. [15]
  Long TANG , Yaxin BIAN , Luyuan CHEN , Xiangyang HOU , Xiao WANG , Jijiang WANG . Syntheses, structures, and properties of three coordination polymers based on 5-ethylpyridine-2,3-dicarboxylic acid and N-containing ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1975-1985. doi: 10.11862/CJIC.20240180
16. [16]
  Changzhu Huang , Wei Dai , Shimao Deng , Yixin Tian , Xiaolin Liu , Jia Lin , Hong Chen . A self-cleaning window for high-efficiency photodegradation of indoor formaldehyde. Chinese Chemical Letters, 2024, 35(9): 109429-. doi: 10.1016/j.cclet.2023.109429
17. [17]
  Jing Guo , Zhi-Guo Lu , Rui-Chen Zhao , Bao-Ku Li , Xin Zhang . Nucleic acid therapy for metabolic-related diseases. Chinese Chemical Letters, 2025, 36(3): 109875-. doi: 10.1016/j.cclet.2024.109875
18. [18]
  Xiying Wu , Anze Liu , Yuzhong Yan , Ying Lu , Huan Wang . Folic acid ameliorates the immunogenicity of PEGylated liposomes. Chinese Chemical Letters, 2025, 36(6): 110285-. doi: 10.1016/j.cclet.2024.110285
19. [19]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
20. [20]
  Tingting Liu , Pengfei Sun , Wei Zhao , Yingshuang Li , Lujun Cheng , Jiahai Fan , Xiaohui Bi , Xiaoping Dong . Magnesium doping to improve the light to heat conversion of OMS-2 for formaldehyde oxidation under visible light irradiation. Chinese Chemical Letters, 2024, 35(4): 108813-. doi: 10.1016/j.cclet.2023.108813

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(1482)
HTML views(90)

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