Citation: WAND Li-wen, LI Feng-xu, LI Ming-feng, CHU Yang, CHEN Ji-xiang. Effect of H₂S/H₂ sulfuration temperature on performance of MoP/SiO₂ catalyst for thioetherification[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(5): 621-628. shu

Effect of H₂S/H₂ sulfuration temperature on performance of MoP/SiO₂ catalyst for thioetherification

1.
Department of Catalysis Science and Engineering, Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
2.
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Corresponding author: CHEN Ji-xiang, jxchen@tju.edu.cn
Received Date: 17 October 2018
Revised Date: 23 March 2019

Fund Project: The project was supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering RIPP, SINOPECThe project was supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC)

Figures(11)

The MoP/SiO₂ catalyst was prepared from the supported Mo phosphate by the H₂-TPR method and treated with 3%H₂S/H₂ at different temperatures. The as-prepared catalysts were characterized by means of XRD, HRTEM-EDX, XPS, NH₃-TPD, ICP-AES and CO chemisorption and tested for the thioetherification of isoprene and n-butylmercaptan. The effects of sulfuration temperature on the MoP/SiO₂ catalyst structure and thioetherification performance were investigated. The results showed that the MoP phase was still stable even at the sulfuration temperature of 400 ℃. As the sulfuration temperature increased, the acid amount of the catalysts increased while the surface metal site density decreased. As a result, in the thioetherification of isoprene and n-butylmercaptan, the C-S bond hydrogenolysis and the over-hydrogenation of isoprene were suppressed on the sulfurized catalysts, while the olefin polymerization was promoted. Relatively, the MoP/SiO₂ catalyst sulfurized at 120 ℃ had better performance for the thioetherification and the selective hydrogenation of isoprene.
- molybdenum phosphide,
- sulfuration temperature,
- thioetherification,
- selective hydrogenation
1. [1]
  BRUNET S, MEY D, PÉROT G, BOUCHY G, DIEHL F. On the hydrodesulfurization of FCC gasoline:A review[J]. Appl Catal A:Gen, 2005,278(2):143-172. doi: 10.1016/j.apcata.2004.10.012
2. [2]
  SONGC . Anoverviewofnewapproachestodeepdesulfurizationforultra-cleangasoline, dieselfuelandjetfuel[J]. Catal Today, 2003,86(1):211-263.
3. [3]
  PETTITI I, BOTTO I L, CABELLO C I, COLONNA C, FATICANTI M, MINELLI G, PORTA P, THOMAS H J. Anderson-type heteropolyoxomolybdates in catalysis 2. EXAFS study on λ-Al₂O₃-supported Mo, Co and Ni sulfided phases as HDS catalysts[J]. Appl Catal A:Gen, 2001,220(1):113-121.
4. [4]
  MENG Xiang-dong, ZHOU Hong-tao, SUN Shou-hua. Process selection of selective hydrodesulfurization unit of catalytic cracking gasoline[J]. Petrochem Technol Appl, 2014,32(4):332-336. doi: 10.3969/j.issn.1009-0045.2014.04.012
5. [5]
  XIAO Zhao-jin, HUANG Xing-liang. Study of mercaptans and isoprene thioetherfication reaction on nickel catalyst[J]. J Mol Catal (China), 2005,19(4):280-284. doi: 10.3969/j.issn.1001-3555.2005.04.009
6. [6]
  XIAO Zhao-jin, HUANG Xing-liang. Effect of preparation conditions on the catalytic properties of Ni/Al₂O₃ catalyst in the diene thioetherfication reaction[J]. Petrochem Technol, 2004,33(s1):381-382.
7. [7]
  XIAO Zhao-jin, HUANG Xing-liang, TONG Zong-wen. Effect of preparation conditions on the catalytic properties of Ni/Al₂O₃ catalyst in the diene thioetherfication reaction[J]. Pet Process Petrochem, 2006,37(5):24-28. doi: 10.3969/j.issn.1005-2399.2006.05.006
8. [8]
  SHEN Zhi-bing, KE Ming, ZHANG Jun-tao, ZHANG Zhi-ping, LIANG Sheng-rong. Catalytic performance of Mo-Ni/Al₂O₃ for thioetherfication of FCC gasoline[J]. Acta Pet Sin(Pet Process Sect), 2015,31(6):1269-1274. doi: 10.3969/j.issn.1001-8719.2015.06.003
9. [9]
  SHEN Z B, KE M, YU P, HU H Q, SONG Z Z, JIANG Q Z. Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al₂O₃ catalysts[J]. J Mol Catal A:Chem, 2015,396:120-127. doi: 10.1016/j.molcata.2014.09.034
10. [10]
  SHEN Z B, KE M, YU P, LIU S D, SONG Z Z, JIANG Q Z. Catalytic activities of mo-modified Ni/Al₂O₃ catalysts for thioetherification of mercaptans and di-olefins in fluid catalytic cracking naphtha[J]. Transition Met Chem, 2012,37(6):587-593. doi: 10.1007/s11243-012-9625-0
11. [11]
  HUANG D Q, KE M, BAO X J, LIU H Y. Fe-promoted Ni/Al₂O₃ thioetherification catalysts with enhanced low temperature activity for removing mercaptans from liquefied petroleum gas[J]. Ind Eng Chem Res, 2016,55(5):1192-1201. doi: 10.1021/acs.iecr.5b03797
12. [12]
  OYAMA S T. Novel catalysts for advanced hydroprocessing:Transition metal phosphides[J]. J Catal, 2003,216(1):343-352.
13. [13]
  OYAMA S T, GOTT T, ZHAO H Y, LEE Y K. Transition metal phosphide hydroprocessing catalysts:A review[J]. Catal Today, 2009,143(1):94-107.
14. [14]
  LEE Y K, OYAMA S T. Bifunctional nature of a SiO₂ -supported Ni₂P catalyst for hydrotreating:EXAFS and FTIR studies[J]. J Catal, 2006,239(2):376-389. doi: 10.1016/j.jcat.2005.12.029
15. [15]
  CHEN J X, SHI H, LI L, LI K L. Deoxygenation of methyl laurate as a model compound to hydrocarbons on transition metal phosphide catalysts[J]. Appl Catal B:Environ, 2014,144(2):870-884.
16. [16]
  REN T Y, LI M F, CHU Y, CHEN J X. Thioetherification of isoprene and butanethiol on transition metal phosphides[J]. J Energy Chem, 2018,27(3):930-939. doi: 10.1016/j.jechem.2017.07.017
17. [17]
  PHILLIPS D C, SAWHILL S J, SELF R, BUSSELL M E. Synthesis, characterization, and hydrodesulfurization properties of silica-supported molybdenum phosphide catalysts[J]. J Catal, 2002,207(2):266-273.
18. [18]
  CHEN J X, YANG Y, SHI H, LI M F, CHU Y, PAN Z Y, YU X B. Regulating product distribution in deoxygenation of methyl laurate on silica-supported Ni-Mo phosphides:Effect of Ni/Mo ratio[J]. Fuel, 2014,129(7):1-10.
19. [19]
  LI K L, WANG R J, CHEN J X. Hydrodeoxygenation of anisole over silica-supported Ni₂P, MoP, and NiMoP catalysts[J]. Energy Fuels, 2011,25(3):854-863. doi: 10.1021/ef101258j
20. [20]
  ZHANG Z N, TANG M X, CHEN J X. Effects of P/Ni ratio and Ni content on performance of λ-Al₂O₃-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons[J]. Appl Surf Sci, 2016,360(4):353-364.
21. [21]
  SUN F X, WU W C, WU Z L, GUO J, WEI Z B, YANG Y X, JIANG Z X, TIAN F P, LI C. Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported MoP, Ni₂P, and NiMoP catalysts[J]. J Catal, 2004,228(2):298-310. doi: 10.1016/j.jcat.2004.09.002
22. [22]
  WU Z L, SUN F X, WU W C, FENG Z C, LIANG C H, WEI Z B, LI C. On the surface sites of MoP/SiO₂ catalyst under sulfiding conditions:Ir spectroscopy and catalytic reactivity studies[J]. J Catal, 2004,222(1):41-52.
23. [23]
  BAI J, LI X, WANG A J, PRINS R WANG Y. Different role of H₂S and dibenzothiophene in the incorporation of sulfur in the surface of bulk MoP during hydrodesulfurization[J]. J Catal, 2013,300(3):197-200.
24. [24]
  SHEN Z B, KE M, YU P, HU H Q, SONG Z Z, JIANG Q Z. Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al₂O₃catalysts[J]. J Mol Catal A:Chem, 2015,396:120-127. doi: 10.1016/j.molcata.2014.09.034
25. [25]
  WILSON R L, KEMBALL C. Catalytic reactions of methyl mercaptan on disulfides of molybdenum and tungsten[J]. J Catal, 1964,3(5):426-437. doi: 10.1016/0021-9517(64)90145-9
26. [26]
  ZHOU Zi-yuan, HUANG Xing-liang, ZHANG Yan, LI Jian. Study on the acid catalysts for diene thioetherification[C]//National Youth Catalysis Conference. Beijing: China Petrochemical Press, 2007.
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沈阳化工大学材料科学与工程学院沈阳 110142

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Effect of H₂S/H₂ sulfuration temperature on performance of MoP/SiO₂ catalyst for thioetherification