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. shu

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

State Key Laboratory of Heavy Oil Processing, China University of Petroleum(East China), Qingdao 266580, China

Corresponding author: ZHANG Kong-yuan, zkyuana@126.com
Received Date: 25 September 2017
Revised Date: 8 January 2018

Figures(6)

(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.
- sulfur-tolerant shift catalyst,
- ex-situ presulfurization technology,
- (NH₄)₂S,
- Na₂S
1. [1]
  RATNASAMY C, WAGNER J P. Water gas shift catalysis[J]. Cat Rev, 2009,51(3):325-440. doi: 10.1080/01614940903048661
2. [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. [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.
4. [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.
5. [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.
6. [6]
  XU Shi-ye. Research and development on presulfurizing agent for catalytic hydrogenation[D]. Xi`an: Xi`an Shiyou University, 2015.
7. [7]
  GUILLAUME D, LOPEZ S, CSERI T. Process for sulfurization of catalysts for hydrotreatment: US, US7513990[P]. 2009.
8. [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. [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.
10. [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.
11. [11]
  SEAMANS J D, WELCH J G, GASSER N G. Method of presulfiding a hydrotreating catalyst: US, US4943547[P]. 1990.
12. [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. [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. [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. [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. [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. [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. [18]
  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.
19. [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. [20]
  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.
21. [21]
  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.
1. [1]
  Ziyi Xiao , Xinyi Ma , Linping Wang , Haobin Hu , Enzhou Liu . Efficient photocatalytic conversion H₂S over NiS₂/twinned-Mn_0.5Cd_0.5S Schottky/S-scheme homojunction in Na₂S/Na₂SO₃ solution. Acta Physico-Chimica Sinica, 2026, 42(4): 100171-0. doi: 10.1016/j.actphy.2025.100171
2. [2]
  Shuang Zhao , Fei Jia , Kaibei Zhan , Rui-Xi Wang , Pengfei Tan , Lin Shen , Li-Ming Wu , Ling Chen . Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A₂(H₃C₃N₄S₂)₂•H₂O (A =NH₄, K, Rb, Cs). Chinese Chemical Letters, 2026, 37(3): 110625-. doi: 10.1016/j.cclet.2024.110625
3. [3]
  Fan Fan , Hao Xiu , Yuting Wang , Yongpeng Cui , Yajun Wang . Construction of NH₂-MIL-125/Na-doped g-C₃N₄ composite S-scheme heterojunction and its performance in photocatalytic hydrogen peroxide production. Acta Physico-Chimica Sinica, 2026, 42(2): 100143-0. doi: 10.1016/j.actphy.2025.100143
4. [4]
  Jiali Lei , Juan Wang , Wenhui Zhang , Guohong Wang , Zihui Liang , Jinmao Li . TiO₂/CdIn₂S₄ S-scheme heterojunction photocatalyst promotes photocatalytic hydrogen evolution coupled vanillyl alcohol oxidation. Acta Physico-Chimica Sinica, 2025, 41(12): 100174-0. doi: 10.1016/j.actphy.2025.100174
5. [5]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-0. doi: 10.1016/j.actphy.2025.100064
6. [6]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
7. [7]
  Yilin Cui , Zhongfu Li , Weikun Zhang , Yu Gao , Zhichao Dong , Conghua Liu . Sulfur vacancies boosting C₂H₄ selectivity of 2D/2D In_2.77S₄/CuInS₂ S-scheme heterojunction for CO₂ photoreduction. Acta Physico-Chimica Sinica, 2026, 42(7): 100274-. doi: 10.1016/j.actphy.2026.100274
8. [8]
  Jiaqi Yang , Xuqiang Hao , Jiejie Jing , Yuqiang Hao , Zhiliang Jin . 3D/2D ReSe₂/ZnCdS S-scheme photocatalyst with efficient interfacial charge separation for optimized hydrogen production. Acta Physico-Chimica Sinica, 2025, 41(10): 100131-0. doi: 10.1016/j.actphy.2025.100131
9. [9]
  Ling Zhou , Long Li , Liwen Huang , Yan Wu . Enhanced H₂O₂ production performance via indirect two-electron reduction of HOF/BiVO₄ (010) S-scheme photocatalyst. Acta Physico-Chimica Sinica, 2026, 42(3): 100172-0. doi: 10.1016/j.actphy.2025.100172
10. [10]
  Wenjun Zhu , Chenbin Ai , Kaiqiang Xu , Yatai Zhou , Xidong Zhang , Yong Zhang . WO₃@TP inorganic@organic S-scheme photocatalyst for boosting H₂O₂ production. Acta Physico-Chimica Sinica, 2026, 42(3): 100184-0. doi: 10.1016/j.actphy.2025.100184
11. [11]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
12. [12]
  Chengcheng Yuan , Wei Xia , Jun Wang , Xiaofeng Zhu , Yong Zhang , Bicheng Zhu , Jiaguo Yu . A dual-functional single-atom modified SnS₂/CdS S-scheme photocatalyst for synergistic hydrogen production and lactic acid oxidation: A DFT study. Acta Physico-Chimica Sinica, 2026, 42(6): 100244-0. doi: 10.1016/j.actphy.2026.100244
13. [13]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
14. [14]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-0. doi: 10.3866/PKU.WHXB202312024
15. [15]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
16. [16]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
17. [17]
  Yanyan Zhao , Zhen Wu , Yong Zhang , Bicheng Zhu , Jianjun Zhang . Enhancing photocatalytic H₂O₂ production via dual optimization of charge separation and O₂ adsorption in Au-decorated S-vacancy-rich CdIn₂S₄. Acta Physico-Chimica Sinica, 2025, 41(11): 100142-0. doi: 10.1016/j.actphy.2025.100142
18. [18]
  Liyuan Huang , Shaodan Wang , Lili Wen , Hong Yuan . S型异质结富硫空位Sv-ZnIn₂S₄/TpPa-1的构筑及其光催化制氢研究——推荐一个创新化学实验. University Chemistry, 2026, 41(8): 339-349. doi: 10.12461/PKU.DXHX202508010
19. [19]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Construction of ZnCoP/CdLa₂S₄ Schottky Heterojunctions for Enhancing Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-0. doi: 10.3866/PKU.WHXB202404030
20. [20]
  Jingping Li , Suding Yan , Jiaxi Wu , Qiang Cheng , Kai Wang . Improving hydrogen peroxide photosynthesis over inorganic/organic S-scheme photocatalyst with LiFePO₄. Acta Physico-Chimica Sinica, 2025, 41(9): 100104-0. doi: 10.1016/j.actphy.2025.100104

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(2685)
HTML views(432)

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