Citation: Chen CHEN, Hai-jie LI, Yang BAI, Fu-xiang FENG, Lei TIAN, Yong YANG, Yuan LIU, Qiang GUO. Effect of sulfidation temperature on component transformation and catalytic performance of direct coal liquefaction catalyst[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(1): 54-62. doi: 10.1016/S1872-5813(21)60118-4 shu

Effect of sulfidation temperature on component transformation and catalytic performance of direct coal liquefaction catalyst

Chen CHEN ^1, ,
Hai-jie LI ² ,
Yang BAI ¹ ,
Fu-xiang FENG ² ,
Lei TIAN ² ,
Yong YANG ^{2, 3} ,
Yuan LIU ^1,, ,
Qiang GUO ^{2, 3,,}

1.
School of Chemical Engineering, Tianjin University, Tianjin 300350, China
2.
National Energy Center for Coal to Liquids, Synfuels China Technology Co. Ltd, Beijing 101407, China
3.
Synfuels China Technology (Inner Mongolia) Co. Ltd, Ordos 010300, China

Corresponding author: Yuan LIU, yuanliu@tju.edu.cn Qiang GUO, guoqiang@synfuelschina.com.cn
Received Date: 18 May 2021
Revised Date: 2 June 2021

Figures(7)

A series of iron sulfide catalysts were prepared in 5% H₂S/N₂ atmosphere at different pre-sulfidation temperatures, and their catalytic activity for naphthalene hydrogenation was studied at 360 ℃ in 1% H₂S/H₂ atmosphere at 5 MPa. The component transformation of the catalyst under varied pre-sulfidation temperature and reaction conditions was researched using MES, XRD and XPS. The results revealed that the sulfidation process was in the form of sulfurizing from surface to interior in the order of FeS₂→FeS, Fe_1–xS→Fe₃S₄→Fe₂O₃ during which transferring sulfur to the body phase was benefited from the rise of temperature. After contacting 1% H₂S/H₂ gas, the particles rapidly transformed to Fe_1–xS from outside to the inside. By adjusting sulfidation conditions, the Fe_1–xS content was high while the particle size was small, which made it possible to obtain the greatest activity of the catalyst.
- direct coal liquefaction,
- γ-Fe₂O₃,
- sulfidation,
- component transformation,
- hydrogenation of naphthalene
1. [1]
  GUO M, XU Y. Coal-to-liquids projects in China under water and carbon constraints[J]. Energy Policy,2018,117:58−65. doi: 10.1016/j.enpol.2018.02.038
2. [2]
  LIU Z, GUAN D B, WEI W, DAVIS S J, CIAIS P, BAI J, PENG S S, ZHANG Q, HUBACEK K, MARLAND G, ANDRES R J, CRAWFORD-BROWN D, LIN J T, ZHAO H Y, HONG C P, BODEN T A, FENG K S, PETERS G P, XI F M, LIU J G, LI Y, ZHAO Y, ZENG N, HE K B. Reduced carbon emission estimates from fossil fuel combustion and cement production in China[J]. Nature,2015,524(7565):335−338. doi: 10.1038/nature14677
3. [3]
  SHUI H, CAI Z, XU C. Recent advances in direct coal liquefaction[J]. Energies,2010,3(2):155−170. doi: 10.3390/en3020155
4. [4]
  XIE J, LU H, SHU G, LI K, ZHANG X, WANG H, YUE W, GAO S, CHEN Y. The relationship between the microstructures and catalytic behaviors of iron-oxygen precursors during direct coal liquefaction[J]. Chin J Catal,2018,39(4):857−866. doi: 10.1016/S1872-2067(17)62919-X
5. [5]
  HIRANO K, KOUZU M, OKADA T, KOBAYASHI M, IKENAGA N, SUZUKI T. Catalytic activity of iron compounds for coal liquefaction[J]. Fuel,1999,78(15):1867−1873. doi: 10.1016/S0016-2361(99)00095-2
6. [6]
  IKENAGA N-O, UEDA C, MATSUI T, OHTSUKI M, SUZUKI T. Co-liquefaction of micro algae with coal using coal liquefaction catalysts[J]. Energy Fuels,2001,15(2):350−355. doi: 10.1021/ef000129u
7. [7]
  MONTANO P A, VAISHNAVA P P, KING J A, EISENTROUT E N. Mössbäuer study of decomposition of pyrite in hydrogen[J]. Fuel,1981,60(8):712−716. doi: 10.1016/0016-2361(81)90224-6
8. [8]
  IKENAGA N-O, TANIGUCHI H, WATANABE A, SUZUKI T. Sulfiding behavior of iron based coal liquefaction catalyst[J]. Fuel,2000,79(3):273−283.
9. [9]
  HUFFMAN G P, GANGULY B, ZHAO J, RAO K R P M, SHAH N, FENG Z, HUGGINS F E, TAGHIEI M M, LU F. Structure and dispersion of iron-based catalysts for direct coal liquefaction[J]. Energy Fuels,1993,7(2):285−296. doi: 10.1021/ef00038a020
10. [10]
  KANEKO T, TAZAWA K, KOYAMA T, SATOU K, SHIMASAKI K, KAGEYAMA Y. Transformation of iron catalyst to the active phase in coal liquefaction[J]. Energy Fuels,1998,12(5):897−904. doi: 10.1021/ef9702310
11. [11]
  KANEKO T, SUGITA S, TAMURA M, SHIMASAKI K, MAKINO E, SILALAHI L H. Highly active limonite catalysts for direct coal liquefaction[J]. Fuel,2002,81(11/12):1541−1549. doi: 10.1016/S0016-2361(02)00079-0
12. [12]
  GUO Gui-gui. Analysis of catalyst vulcanization of coal direct liquefaction to oil hydrogenation modification combination[J]. Energy Sci Technol,2013,11(6):68−72. doi: 10.3969/j.issn.1674-8492.2013.06.022
13. [13]
  WANG Zhong-yi, YAN Zuo-jie, SHAN Min, CHEN Ping-ping, TONG Jian. Application summary of start-up technology of ex-situ presulfiding hydrocracking catalyst[J]. Pet Refin Eng,2021,51(1):10−12+32. doi: 10.3969/j.issn.1002-106X.2021.01.003
14. [14]
  SUN Xin-xin, YUAN Ming-yao, WU Xue-qing. Study on ex-situ presulfurization of selective hydrogenation catalyst[J]. Pet Refin Eng,2020,50(12):42−45. doi: 10.3969/j.issn.1002-106X.2020.12.012
15. [15]
  TAO Shuai-jiang. Progress in presulfurization technology for hydrotreating catalyst[J]. Angang Technol,2020,(4):9−12. doi: 10.3969/j.issn.1006-4613.2020.04.002
16. [16]
  ZHANG Li, FAN Wen-qing, XIAO Wen-can, XU Lin, LIU Chang-kun. Study on the technology of pre-sulfurization for hydrogenated catalyst[J]. Guangdong Chem Ind,2020,47(12):126−127. doi: 10.3969/j.issn.1007-1865.2020.12.053
17. [17]
  JIN Ji-hai, LIU Li-zhi, SONG Jun-hui, JIAO Zu-kai, YAN Jin-long, ZHEN Tao, ZHANG Duo. Study on hydrodeacidification performance of off-site pre-sulfidation catalysts[J]. Inorg Chem Ind,2020,52(9):100−104.
18. [18]
  DE WIND M, HEINERMAN J J L, LEE S L, PLANTENGA F L. Air quality and economics spur use of presulfided catalysts[J]. Oil Gas J,1992,90(8):49−53.
19. [19]
  DJEGA-MARIADASSOU G, BESSON M, BRODZKI D, CHARCOSSET H, TRAN VINH H, VARLOUD J. Evolution of highly dispersed catalysts during hydroliquefaction of coal[J]. Fuel Process Technol,1986,12:143−153. doi: 10.1016/0378-3820(86)90072-X
20. [20]
  LAMBERT J M, SIMKOVICH G, WALKER P L. Production of pyrrhotites by pyrite reduction[J]. Fuel,1980,59(10):687−690. doi: 10.1016/0016-2361(80)90019-8
21. [21]
  KONDORO J W A. Mossbauer study of vacancies in natural pyrrhotite[J]. J Alloys Compd,1999,289(1/2):36−41. doi: 10.1016/S0925-8388(99)00170-X
22. [22]
  JEANDEY C, ODDOU J L, MATTEI J L, FILLION G. Mössbauer investigation of the pyrrhotite at low temperature[J]. Solid State Commun,1991,78(3):195−198. doi: 10.1016/0038-1098(91)90282-Z
23. [23]
  CHANG L, ROBERTS A P, TANG Y, RAINFORD B D, MUXWORTHY A R, CHEN Q W. Fundamental magnetic parameters from pure synthetic greigite (Fe₃S₄)[J]. J Geophys Res-Sol Ea,2008,113(B6):1−16.
24. [24]
  CUDA J, KOHOUT T, TUCEK J, FILIP J, MALINA O, KRIZEK M, ZBORIL R. Mossbauer Spectroscopy in Materials Science[M]. New York: AIP Publishing, 2014: 8−11.
25. [25]
  MONTANO P A, SEEHRA M S. Magnetism of iron pyrite (FeS₂) - a Mossbauer study in an external magnetic-field[J]. Solid State Commun,1976,20(9):897−898. doi: 10.1016/0038-1098(76)91300-4
26. [26]
  OH S J, COOK D C, TOWNSEND H E. Characterization of iron oxides commonly formed as corrosion products on steel[J]. Hyperfine Interact,1998,112(1/4):59−65.
27. [27]
  KOBZI B, WATANABE Y, AKIYAMA K, KUZMANN E, HOMONNAY Z, KREHULA S, RISTIĆ M, NISHIDA T, KUBUKI S. ⁵⁷Fe-Mössbauer study and methylene blue decomposing effect of nanoparticle mixtures composed of metallic iron and maghemite[J]. J Alloys Compd,2017,722:94−100. doi: 10.1016/j.jallcom.2017.06.083
28. [28]
  KUBONO I, NISHIDA N, KOBAYASHI Y, YAMADA Y. Mossbauer spectra of iron (III) sulfide particles[J]. Hyperfine Interact,2017,238:1−10. doi: 10.1007/s10751-016-1375-5
29. [29]
  ZHAO R, YANG L, SONG X, ZHANG W, WANG B, HUANG S, WU S, WU Y. Effects of sulfur additive on the transformation behaviors of γ-Fe₂O₃ and coal liquefaction performances under mild conditions[J]. Asia-Pac J Chem Eng,2018,13(4):1−9.
30. [30]
  ZUO W B, PELENOVICH V, LI Q D, ZENG X M, FU D J. Study on velocity mode of Fe-57 Mossbauer spectroscopy and determination of lattice dynamics in Fe₃S₄[J]. Results Phys,2019,12:1214−1217. doi: 10.1016/j.rinp.2019.01.010
31. [31]
  SKINNER B J, GRIMALDI F S, ERD R C. Greigite thio-spinel of iron-new mineral[J]. Am Mineral,1964,49(5/6):543−555.
32. [32]
  SADEGH-VAZIRI R, BABLER M U. Removal of hydrogen sulfide with metal oxides in packed bed reactors-a review from a modeling perspective with practical implications[J]. Appl Sci-Basel,2019,9(24):1−24.
33. [33]
  MORRISH R, SILVERSTEIN R, WOLDEN C A. Synthesis of stoichiometric FeS₂ through plasma-assisted sulfurization of Fe₂O₃ nanorods[J]. J Am Chem Soc,2012,134(43):17854−17857. doi: 10.1021/ja307412e
34. [34]
  YU L, LANY S, KYKYNESHI R, JIERATUM V, RAVICHANDRAN R, PELATT B, ALTSCHUL E, PLATT H A S, WAGER J F, KESZLER D A, ZUNGER A. Iron chalcogenide photovoltaic absorbers[J]. Adv Energy Mater,2011,1(5):748−753. doi: 10.1002/aenm.201100351
35. [35]
  JAGADEESH M S, SEEHRA M S. Thermomagnetic studies of conversion of pyrite and marcasite in different atmospheres (vacuum, H₂, He And CO)[J]. J Phys D Appl Phys,1981,14(11):2153−2167. doi: 10.1088/0022-3727/14/11/023
36. [36]
  HONG Y, FEGLEY B. The kinetics and mechanism of pyrite thermal decomposition[J]. Ber Bunsen-Ges Phys,1997,101(12):1870−1881. doi: 10.1002/bbpc.19971011212
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