Volume 46 Issue 3
Mar.  2018
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ZHANG Kong-yuan, CHEN Yan-fei, FAN Si-qiang, CUI Cheng-xin, XIAO Chang-lin, LIU Chen-guang. Study on ex-situ presulfurization technologies with different presulfiding agents for CoMo-based sulfur-tolerant shift catalysts[J]. Journal of Fuel Chemistry and Technology, 2018, 46(3): 346-354.
Citation: ZHANG Kong-yuan, CHEN Yan-fei, FAN Si-qiang, CUI Cheng-xin, XIAO Chang-lin, LIU Chen-guang. Study on ex-situ presulfurization technologies with different presulfiding agents for CoMo-based sulfur-tolerant shift catalysts[J]. Journal of Fuel Chemistry and Technology, 2018, 46(3): 346-354.

Study on ex-situ presulfurization technologies with different presulfiding agents for CoMo-based sulfur-tolerant shift catalysts

  • Received Date: 2017-09-25
  • Rev Recd Date: 2018-01-08
  • Available Online: 2021-01-23
  • Publish Date: 2018-03-10
  • (NH4)2S and Na2S were selected from several presulfiding agents. Industrial Co-Mo based sulfur-tolerant shift catalysts were ex-situ presulfided with different presulfurization technologies. The crystal structures, surface characteristics and micro appearance were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (HRTEM). (NH4)2S and Na2S as presulfiding agents did not show obvious effects on the crystal structures of the catalysts. Partial O-S exchange of the active components was observed when (NH4)2S was used for presulfirization. And when presulfided with Na2S, the active components still remained oxidation state. As the ex-situ presulfurization temperature increased, the extent of vulcanization was:S-Na2S > S-(NH4)2S > the general in situ pre-vulcanization. When presulfided with (NH4)2S or the general in situ pre-vulcanization, the stacking number of MoS2 layers was mainly two to three. And when presulfided with Na2S, the stacking number of MoS2 layers increased obviously, mostly three to five. The activity sequence of the catalysts was S-Na2S > S-(NH4)2S > the general in situ pre-vulcanization when the catalysts were tested in a micro-fixed reactor at temperatures of 285, 350 and 450℃ respectively.
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  • [1]
    RATNASAMY C, WAGNER J P. Water gas shift catalysis[J]. Cat Rev, 2009, 51(3):325-440. doi: 10.1080/01614940903048661
    [2]
    GE H, LI X K, Wang J G, LU Z J, QIN Z F, ZHOU L G. Study on hydrodesulfurization of thiophene over Mo/Al2O3 catalyst presulfided by thiosulfate ammonium[J]. J Fuel Chem Technol, 2009, 37(2):199-204. doi: 10.1016/S1872-5813(09)60016-5
    [3]
    LIU B, CHAI Y M, WANG Y J, ZHANG T T, LIU Y Q, LIU C G. A simple technique for preparation of presulfided eggshell MoS2/Al2O3 catalysts and kinetics approach for highly selective hydrodesulfurization of FCC gasoline[J]. Appl Catal, A, 2010, 388(1/2):248-255. http://www.sciencedirect.com/science/article/pii/S0926860X1000640X
    [4]
    CHOUZIER S, VRINAT M, CSREI T, ROY-AUBERGER M, AFANASIEV P. HDS and HDN activity of (Ni, Co)Mo binary and ternary nitrides prepared by decomposition of hexamethylenetetramine complexes[J]. Appl Catal, A, 2011, 400(1/2):82-90. doi: 10.1021/jp002133c
    [5]
    LI Y P, LIU D P, LIU C G. Hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performance of an ex situ presulfided MoNiP/Al2O3 catalyst:Model compounds study and pilot test for fluidized catalytic cracking (FCC) diesel oil[J]. Energy Fuels, 2010, 24(2):820-829. doi: 10.1021/ef901084f
    [6]
    许世业. 加氢催化预硫化剂的研究与开发[D]. 西安: 西安石油大学, 2015.

    XU Shi-ye. Research and development on presulfurizing agent for catalytic hydrogenation[D]. Xi`an: Xi`an Shiyou University, 2015.
    [7]
    GUILLAUME D, LOPEZ S, CSERI T. Process for sulfurization of catalysts for hydrotreatment: US, US7513990[P]. 2009.
    [8]
    GAO Y L, FANG X C, CHENG Z M. Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China[J]. Front Chem Sci Eng, 2011, 5(3):287-296. doi: 10.1007/s11705-010-0529-2
    [9]
    GAO Y L, FANG X C, CHENG Z M. A comparative study on the ex situ and in situ presulfurization of hydrotreating catalysts[J]. Catal Today, 2010, 158(3):496-503. https://www.sciencedirect.com/science/article/pii/S0920586110004815
    [10]
    LIAN Y X, WANG H F, FANG W P, YANG Y Q. Water gas shift activity of Co-Mo/MgO-Al2O3 catalysts presulfided with ammonium sulfide[J]. Energy Chem, 2010, 19(1):61-66. http://dl.acm.org/citation.cfm?id=2355575.2356857
    [11]
    SEAMANS J D, WELCH J G, GASSER N G. Method of presulfiding a hydrotreating catalyst: US, US4943547[P]. 1990.
    [12]
    RATNASAMY P, RODRIQUE L, LEONARD A J. Structural and textural studies in molybdenum sulfide systems[J]. J Phys Chem, 1973, 77(18):2242-2245. doi: 10.1021/j100637a017
    [13]
    CHIANELLI R R, PRESTRIDGE E B, PECORARO T A, DENEUFVILLE J P. Molybdenum disulfide in the poorly crystalline "rag" structure[J]. Science, 1979, 203(4385):1105-1107. doi: 10.1126/science.203.4385.1105
    [14]
    MOSES P G, HINNEMANN B, TOPSØE H, NØRSKOV J K. The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions:A density functional study[J]. J Catal, 2007, 248(2):188-203. doi: 10.1016/j.jcat.2007.02.028
    [15]
    ABART J, DELGADO E, ERTL G, JEZIOROWSKI H, KNÖZINGER H, THIELE N, WANG X Z H, TAGLAUER E. Surface structure and reduction behaviour of Nio-MoO3/Al2O3 catalysts[J]. Appl Catal, 1982, 2(3):155-176. doi: 10.1016/0166-9834(82)80198-X
    [16]
    WANG C M, TSAI T C, WANG I. Deep hydrodesulfurization over Co/Mo catalysts supported on oxides containing vanadium[J]. J Catal, 2009, 262(2):206-214. doi: 10.1016/j.jcat.2008.12.012
    [17]
    QIU L, XU G. Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts[J]. Appl Surf Sci, 2010, 256(11):3413-3417. doi: 10.1016/j.apsusc.2009.12.043
    [18]
    户安鹏, 聂红, 陈文斌, 龙湘云.柠檬酸对CoMo/Al2O3催化剂中助剂作用的影响[J].石油炼制与化工, 2015, 46(9):1-6. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201509001.htm

    HU An-peng, NIE Hong, CHEN Wen-bin, LONG Xiang-yun. Influence of citric acid on promoter role in CoMo/Al2O3 catalyst[J]. Pet Process Petroc, 2015, 46(9):1-6. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201509001.htm
    [19]
    GRIGOR V V V, GEL MAN V N, SOBOLEVSKⅡ V S, KREINDEL A I, GOLOSMAN E Z, SALOMATIN G I, DANTSIG G A, ABDULLAEV T R, LAFER L I, TAKERSON V I. Study of reaction mechanism for conversion of carbon monoxide and steam on copper catalysts employing mass spectrometry and IR spectroscopy[J]. Russ Chem Bull, 1978, 27(5):1015-1017. doi: 10.1007/BF00929015
    [20]
    柴永明, 南军, 相春娥, 柳云骐, 刘晨光.以硫化态前驱物制备的NiMoS/γ-Al2O3催化剂表面活性相HRTEM研究[J].石油学报(石油加工), 2007, 23(3):20-26. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200703003.htm

    CHAI Yong-ming, NAN Jun, XIANG Chun-e, LIU Yun-qi, LIU Chen-guang. Investigation of active phase of NiMoS/γ-Al2O3 prepared by thiosalt as precursor through HRTEM[J]. Acta Petrol Sinica(Pet. Process Sec., 2007, 23(3):20-26. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200703003.htm
    [21]
    贺胜如, 袁赞根, 刘建平.加氢催化剂器外预硫化技术的工业应用[J].石油炼制与化工, 2004, 35(8):34-36. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200507000.htm

    HE Sheng-ru, YUAN Zan-gen, LIU Jian-ping. Commercial application of hydrogenation catalyst with external presulfurizing technology[J]. Pet Process Petroc, 2004, 35(8):34-36. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200507000.htm
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