Citation: YAN Jing-sen, WANG Ze-qing, E Yong-sheng, TANG Jun-jie, AI Li-mei, GAO Jun-feng. Synthesis and deep oxidative desulfurization of vanadium-substituted polyoxotungstate phase transfer catalyst[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(11): 1337-1345. shu

Synthesis and deep oxidative desulfurization of vanadium-substituted polyoxotungstate phase transfer catalyst

School of Biomedical & Chemical Engineering, Liaoning Institute of Science and Technology, Benxi 117004, China

Corresponding author: YAN Jing-sen, yanjs910@163.com
Received Date: 10 June 2019
Revised Date: 10 September 2019

Fund Project: the Key Projects of Natural Science Foundation of Liaoning Province 20180550114PhD Research Startup Foundation of Liaoning Institute of Science and Technology 1810B06The projecct was supported by the Key Projects of Natural Science Foundation of Liaoning Province (20170540475, 20180550114), PhD Research Startup Foundation of Liaoning Institute of Science and Technology (1810B08, 1810B06)and Undergraduate Training Programms for Innovation and Entrepreneurship of Liaoning Institute of Science and Technology (201911430056)PhD Research Startup Foundation of Liaoning Institute of Science and Technology 1810B08the Key Projects of Natural Science Foundation of Liaoning Province 20170540475Undergraduate Training Programms for Innovation and Entrepreneurship of Liaoning Institute of Science and Technology 201911430056

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A series of phase transfer catalysts, composed of vanadium-substituted phosphotungstic acid(H₄[PW₁₁VO₄₀]) and different quaternary cationics were synthesized through ion exchange method. The characterization of FT-IR spectroscopy and X-ray diffraction confirmed that the integrity of polyoxometalate anions and quaternary ammonium cations immobilized in the phase transfer catalyst. The as-prepared catalysts were applied to the catalytic oxidative desulfurization of model diesel oil using H₂O₂ as oxidant. The influencing factors such as quaternary cationics species, catalyst composition, catalyst amount, oxygen-sulfur ratio and reaction temperature were investigated.[(C₁₆H₃₃(CH₃)₃)N]₃H[PW₁₁VO₄₀] is found to be efficient and reusable catalyst for oxidative desulfurization reaction. Under the optimized reaction conditions of n(catalyst)/n(model diesel)=1:80, n(H₂O₂)/n(model diesel)=8:1, 50℃, 3 h, the catalyst exhibits the dibenzothiophene conversion of 100% and excellent reusability with 99.7% conversion after five times reaction. The catalyst and reactants form a microemulsion system and behave like homogeneous mixture during reaction, but precipitates with biphase separation when the reaction ends. The catalyst could be quickly separated and recycled by centrifugation.
- oxidative desulfurization,
- vanadium-substituted phosphotungstic acid,
- phase transfer catalyst
1. [1]
  BANISHARIF F, DEHGHANI M R, CAMPOS-MARTIN J M. Oxidative desulfurization of diesel using vanadium-substituted dawson-type emulsion catalysts[J]. Energy Fuels, 2017,31(5):5419-5427. doi: 10.1021/acs.energyfuels.6b02791
2. [2]
  SONG C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J]. Catal Today, 2003,86(1):211-263.
3. [3]
  ABRO R, GAO S R, CHEN X C. Oxidative desulfurization of gasoline by ionic liquids coupled with extraction by organic solvents[J]. J Brazil Chem Soc, 2016,27(6):998-1006.
4. [4]
  WANG D, EIKA W Q, AMANO H, OKATA K, LSHIHARA A, KABE T. Oxidative desulfurization of fuel oil Part Ⅰ. Oxidation of dibenzothiophenes using tert-butyl hydroperoxide[J]. Appl Catal A:Gen, 2003,253(1):91-99. doi: 10.1016/S0926-860X(03)00528-3
5. [5]
  OTSUKI S, NONAKA T, TAKASHIMA N, QIAN W, LSHIHARA A, LMAI T, KABE T. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction[J]. Energy Fuels, 2000,14(6):1234-1239.
6. [6]
  LIANG W D, ZHANG S, LI H F, ZHANG G. Oxidative desulfurization of simulated gasoline catalyzed acetic acid-based ionice liquids at room temperature[J]. Fuel Process Technol, 2013,109(2):27-31.
7. [7]
  SHIRAISHI Y, NAITO T, HIRAI T. Vanadosilicate molecular sieve as a catalyst for oxidative desulfurization of light oil[J]. Ind Eng Chem Res, 2003,42(24):6034-6039. doi: 10.1021/ie030328b
8. [8]
  WANG R, ZHANG G, ZHAO H. Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil[J]. Catal Today, 2010,149(1/2):15358-15359.
9. [9]
  BANISHARIF F, DEHGHANI M R, CAPEL-SANCHEZ M C, CAMPOS-MARTIN J M. Desulfurization of fuel by extraction and catalytic oxidation using a vanadium substituted dawson-type emulsion catalyst[J]. Ind Eng Chem Res, 2017,56(14):3839-3852. doi: 10.1021/acs.iecr.7b00089
10. [10]
  MAHDIEH S, BABAK M, HAMID R M, KUROSH T H, ALI S, MOJTABA M. Oxidative desulfurization of diesel fuel using a bronsted acidic ionic liquid supported on silica gel[J]. Energy Fuels, 2017,31(9):10196-10205. doi: 10.1021/acs.energyfuels.6b03505
11. [11]
  LI S W, GAO R M, ZHAO J S. Deep oxidative desulfurization of fuel catalyzed by modified heteropolyacid:The comparison performance of three kinds of ionic liquids[J]. ACS Sustainable Chem Eng, 2018,6(11):15858-15866. doi: 10.1021/acssuschemeng.8b04524
12. [12]
  ZHANG J, WANG A J, LI X, MA X H. Oxidative desulfurization of dibenzothiophene and diesel over[Bmim]₃PMo₁₂O₄₀[J]. J Catal, 2011,279(2):269-275.
13. [13]
  HUA Z, BAKER G A. Oxidative desulfurization of fuels using ionic liquids[J]. Front Chem Sci Eng, 2015,9(3):262-279. doi: 10.1007/s11705-015-1528-0
14. [14]
  WANG En-bo. Guidance to Polyoxometalates[M]. Beijing:Chemical Industry Press, 1998.
15. [15]
  ZHANG Hai-yan, DAI Yue-li, CAI Lei. Research progress of heteropoly acid catalyzed oxidative desulfurization[J]. Chem Ind Eng Prog, 2013,32(4):809-815.
16. [16]
  TE M, FAIRBRIDGE C, RING Z. Oxidation reactivities of dibenzothiophenes in polyoxometalate-H₂O₂ and formic acid-H₂O₂ systems[J]. Appl Catal A:Gen, 2001,219:267-280. doi: 10.1016/S0926-860X(01)00699-8
17. [17]
  LI B, LIU Z, HAN C. In situ synthesis, characterization, and catalytic performance of tungtophosphoric acid encapsulated into the framework of mesoporous silica pillared clay[J]. J Colloid Interf Sci, 2012,377(1):334-341. doi: 10.1016/j.jcis.2012.03.067
18. [18]
  ZHANG Y N, WANG L, ZHANG Y L, JIANG Z X, LI C. Ultra-deep oxidative desulfurization of fuel oil catalyzed by dawson-type polyoxotungstate emulsion catalysts[J]. Chin J Catal, 2011,32(1):235-239.
19. [19]
  QI W, WANG Y Z, LI W, WU L X. Surfactant-encapsulated polyoxometalates as immobilized supramolecular catalysts for highly efficient and selective oxidation reactions[J]. Chem Eur J, 2010,16(3):1068-1078. doi: 10.1002/chem.200902261
20. [20]
  HUANG D, ZHAI Z, LU Y C, YANG L M, LUO G S. Optimization of composition of a directly combined catalyst in dibenzothiophene oxidation for deep desulfurization[J]. Ind Eng Chem Res, 2007,46(5):1447-1451. doi: 10.1021/ie0611857
21. [21]
  LI C, JIANG Z X, GAO J B, YANG Y X, WANG S J, TIAN F P, SUN F X, SUN X P, YING P L, HAN C R. Ultra-deep desulfurization of diesel:Oxidation with a recoverable catalyst assembled in emulsion[J]. Chem Eur J, 2004,10(9):2277-2280. doi: 10.1002/chem.200305679
22. [22]
  LI C, GAO J B, JIANG Z G, WANG S G, LU H Y, YANG Y X, JING F. Selective oxidations on recoverable catalysts assembled in emulsions[J]. Top Catal, 2005,35(1/2):169-175.
23. [23]
  ZHANG Y J, GU Y F, DONG X B, WU P F, LI Y L, HU H M, XUE G L. Deep oxidative desulfurization of refractory sulfur compounds with cesium salts of mono-substituted phosphomolybdate as efficient catalyst[J]. Catal Lett, 2017,147(7):1811-1819. doi: 10.1007/s10562-017-2078-5
24. [24]
  LU H Y, GAO J B, JIANG Z X, JING F, YANG Y X, WANG G, LI C. Ultra-deep desulfurization of diesel by selective oxidation with[C₁₈H₃₇N(CH₃)₃]₄[H₂NaPW₁₀O₃₆]catalyst assembled in emulsion droplets[J]. J Catal, 2006,239(2):369-375. doi: 10.1016/j.jcat.2006.01.025
25. [25]
  XU J H, ZHAO S, JI Y C, SONG Y F. Deep desulfurization by amphiphilic lanthanide-containing polyoxometalates in ionic-liquid emulsion systems under mild conditions[J]. Chem Eur J, 2013,19(2):709-715. doi: 10.1002/chem.201202595
26. [26]
  ZHANG Ye-hong. Synthesis, characterization and catalytic performance of keggin type heteropolyacid phase-transfer catalysts[D]. Lanzhou: Lanzhou University of Technology, 2009.
27. [27]
  YAN Jing-sen, AI Li-mei, WANG Qiang, WANG Ze-qing, E Yong-sheng, LIU Hai-bin. Synthesis, characterization and esterification application of acid-functionalized ternary heteropolyanion-based ionic liquids with temperature-responsive behaviour[J]. Chin J Inorg Chem, 2018,34(12):2179-2187. doi: 10.11862/CJIC.2018.272
28. [28]
  WU X F, HUANG T P, TONG X, XIE Z R, CHEN W X, WU Q Y, YAN W F. Thermoregulated polyoxometalate-based ionic-liquid gel electrolytes[J]. RSC Adv, 2015,5(28):21973-21977. doi: 10.1039/C5RA02209F
29. [29]
  WU X F, TONG X, WU Q Y, DING H, YAN W F. Reversible phase transformation-type electrolyte based on layered shape polyoxometalate[J]. J Mater Chem A, 2014,2(16):5780-5784. doi: 10.1039/c3ta15237e
30. [30]
  QI Yue-hong, LIU Qian, LIU Yun-qi, LIU Chen-guang. Synthesis of polytungstozincic quaternary ammonium salts and application in catalytic oxidation desulfurization[J]. Pet Process Pet Chem, 2015,46(6):52-56. doi: 10.3969/j.issn.1005-2399.2015.06.016
31. [31]
  YAMAURA T, KAMATA K, YAMAGUCHI K. Efficient sulfoxidation with hydrogen peroxide catalyzed by a divanadium-subtituted phosphotungstate[J]. Catal Today, 2013,203:76-81. doi: 10.1016/j.cattod.2012.01.026
32. [32]
  WANG Liang. Study on desulfurization of oil catalyzed oxidation by supported heteropoly acid in microemulsion[D]. Qingdao: Ocean University of China, 2011.
33. [33]
  LIU Ri-jia, WANG Rui, KORCHAK V. Synthesis, charaterization and catalytic fuel ultra-deep desulfurization of keggin-type polyoxometalates[J]. Chin J Inorg Chem, 2014,30(3):563-572.
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