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顾佳1 辛忠1,2 高文莉1 何璐铭1 赵瑞1

(1.华东理工大学化工学院上海市多相结构材料化学工程重点实验室, 上海 200237)
(2.华东理工大学化工学院化学工程联合国家重点实验室, 上海 200237)

【摘要】采用等体积浸渍法制备MoS2/Si-ZrO2催化剂,并对其CO耐硫甲烷化的催化活性稳定性进行评估。结果表明在2H2∶2CO∶1N2(摩尔比)、反应压力2.5 MPa、反应温度450℃、硫含量0.01%及质量空速6000 ml/(g·h)的反应条件下,100 h后CO转化率下降11%。深入进行氢气程序升温还原(H2-TPR)、X射线光电子能谱(XPS)、拉曼光谱(RS)、等离子体发射光谱(ICP-OES)、高分辨透射电子显微镜(HRTEM)、热重分析(TGA)以及元素分析等表征后,发现反应后催化剂表面无明显积炭,但出现了明显的团聚现象。而催化剂失活的根本原因是硫流失的发生,导致具有催化活性的桥键S22-物种转变为S2-物种2-H2S。

【关键词】 失活;催化剂;稳定性;天然气;耐硫甲烷化;桥键S22-物种;硫流失;


【基金资助】 国家自然科学基金项目(U1203293,21776091,21808062); 中央高校基本科研业务费专项资金(22A1817025); 上海学科首席科学家项目(10Xd1401500); 中国博士后科学基金项目(2017M611474);

Deactivation behaviors of MoS2/Si-ZrO2 catalyst during sulfur-resistant CO methanation

GU Jia1 XIN Zhong1,2 GAO Wenli1 HE Luming1 ZHAO Rui1

(1.Shanghai Key Laboratory of Multiphase Structure Material Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai, China 200237)
(2.State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai, China 200237)

【Abstract】The MoS2/Si-ZrO2 catalyst was prepared by an equal volume impregnation method, and the catalytic activity stability of the catalyst for CO sulfur-resistant CO methanation was evaluated. The CO conversion of the MoS2/Si-ZrO2 catalyst decreased by 11% under the following conditions: molar ratio of feed gas composition was 2H2:2CO:1N2; concentration of H2S was 0.01%; weight hourly space velocity was 6 000 mL/(g·h); reaction temperature was 450 °C and reaction pressure was 2.5 MPa. The catalysts were further characterized by hydrogen temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS), inductively coupled plasma-optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA) and elemental analysis. The results demonstrated that little carbon deposited on the surface of spent catalyst, which did not cause catalyst deactivation. The minor cause was that MoS2 slabs grew longer and stacked in more layers after long-term reaction and then covered the active sites. The root deactivation cause was attributed to that parts of bridging S22− species with catalytic activity converting to less active S2− species and H2S, which resulted in the loss of active sites and sulfur element.

【Keywords】 deactivation; catalyst; stability; natural gas; sulfur-resistant methanation; bridging S22- species; sulfur loss;


【Funds】 National Natural Science Foundation of China (U1203293, 21776091, 21808062); Fundamental Research Funds for the Central Universities of Ministry of Education of China (22A1817025); Program of Shanghai Subject Chief Scientist (10Xd1401500); China Postdoctoral Science Foundation (2017M611474);

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    [1] Rönsch S, Schneider J, Matthischke S, et al. Review on methanation—from fundamentals to current projects [J]. Fuel, 2016, 166 (2): 276–296.

    [2] Cao H X, Zhang J, Guo C L, et al. Highly dispersed Ni nanoparticles on 3D-mesoporous KIT-6 for CO methanation: effect of promoter species on catalytic performance [J]. Chinese Journal of Catalysis, 2017, 38 (7): 1127–1137.

    [3] Zhang X, Rui N, Jia X, et al. Effect of decomposition of catalyst precursor on Ni/CeO2 activity for CO methanation [J]. Chinese Journal of Catalysis, 2019, 40 (4): 495–503.

    [4] Tao M, Xin Z, Meng X, et al. Highly dispersed nickel within mesochannels of SBA-15 for CO methanation with enhanced activity and excellent thermostability [J]. Fuel, 2017, 188 (1): 267–276.

    [5] Gao J J, Liu Q, Gu F N, et al. Recent advances in methanation catalysts for the production of synthetic natural gas [J]. RSC Advances, 2015, 5 (29): 22759–22776.

    [6] Andersson R, Boutonnet M, Järås S. Higher alcohols from syngas using a K/Ni/MoS2 catalyst: trace sulfur in the product and effect of H2S-containing feed [J]. Fuel, 2014, 115 (1): 544–550.

    [7] Shi G, Han W, Yuan P, et al. Sulfided Mo/Al2O3 hydrodesulfurization catalyst prepared by ethanol-assisted chemical deposition method [J]. Chinese Journal of Catalysis, 2013, 34 (4): 659–666.

    [8] Hao L, Xiong G, Liu L, et al. Preparation of highly dispersed desulfurization catalysts and their catalytic performance in hydrodesulfurization of dibenzothiophene [J]. Chinese Journal of Catalysis, 2016, 37 (3): 412–419.

    [9] Li M, Wang D, Li J, et al. Surfactant-assisted hydrothermally synthesized MoS2 samples with controllable morphologies and structures for anthracene hydrogenation [J]. Chinese Journal of Catalysis, 2017, 38 (3): 597–606.

    [10] Wang B, Yu W, Wang W, et al. Effect of boron addition on the MoO3/CeO2–Al2O3 catalyst in the sulfur-resistant methanation [J]. Chinese Journal of Chemical Engineering, 2018, 26 (3): 509–513.

    [11] Mortensen P M, Gardini D, Damsgaard C D, et al. Deactivation of Ni–MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol [J]. Applied Catalysis A: General, 2016, 523 (8): 159–170.

    [12] Kubička D, Horáček J. Deactivation of HDS catalysts in deoxygenation of vegetable oils [J]. Applied Catalysis A: General, 2011, 394 (1/2): 9–17.

    [13] Vogelaar B M, Steiner P, van Langeveld A D, et al. Deactivation of Mo/Al2O3 and NiMo/Al2O3 catalysts during hydrodesulfurization of thiophene [J]. Applied Catalysis A: General, 2003, 251 (1): 85–92.

    [14] Wang H, Li G L, Rogers K, et al. Hydrotreating of waste cooking oil over supported CoMoS catalyst catalyst-deactivation mechanism study [J]. Molecular Catalysis, 2017, 443 (12): 228–240.

    [15] Li Z, He J, Wang H, et al. Enhanced methanation stability of nano-sized MoS2 catalysts by adding Al2O3 [J]. Frontiers of Chemical Science and Engineering, 2016, 9 (1): 33–39.

    [16] Afanasiev P. The influence of reducing and sulfiding conditions on the properties of unsupported MoS2-based catalysts [J]. Journal of Catalysis, 2010, 269 (2): 269–280.

    [17] Dave M, Rajagopal A, Damm-Ruttensperger M, et al.Understanding homogeneous hydrogen evolution reactivity and deactivation pathways of molecular molybdenum sulfide catalysts [J]. Sustainable Energy & Fuels, 2018, 2 (5): 1020–1026.

    [18] Xi F X, Bogdanoff P, Harbauer K, et al. Structural transformation identification of sputtered amorphous MoSx as an efficient hydrogen-evolving catalyst during electrochemical activation [J].ACS Catalysis, 2019, 9 (3): 2368–2380.

    [19] Gu J, Xin Z, Tao M, et al. Effect of Si-modified zirconia on the properties of MoO3/Si–ZrO2 catalysts for sulfur-resistant CO methanation [J]. Applied Catalysis A: General, 2019, 575 (4): 230–237.

    [20] Gu J, Xin Z, Tao M, et al. Effect of reflux digestion time on MoO3/ZrO2 catalyst for sulfur-resistant CO methanation [J]. Fuel, 2019, 241 (4): 129–137.

    [21] Zhang L, Fu W Q, Xiang M, et al. MgO nanosheet assemblies supported Co Mo catalyst with high activity in hydrodesulfurization of dibenzothiophene [J]. Industrial & Engineering Chemistry Research, 2015, 54 (21): 5580–5588.

    [22] Chang Y H, Nikam R D, Lin C T, et al. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction [J]. ACS Applied Materials Interfaces, 2014, 6 (20): 17679–17685.

    [23] He M, Kong F, Yin G, et al. Enhanced hydrogen evolution reaction activity of hydrogen-annealed vertical MoS2 nanosheets [J]. RSC Advances, 2018, 8 (26): 14369–14376.

    [24] Paul K K, Sreekanth N, Biroju R K, et al. Strongly enhanced visible light photoelectrocatalytic hydrogen evolution reaction in an n-doped MoS2/TiO2 (B) heterojunction by selective decoration of platinum nanoparticles at the MoS2 edge sites [J]. Journal of Materials Chemistry A, 2018, 6 (45): 22681–22696.

    [25] Ma L, Zhou X P, Xu X Y, et al. One-step hydrothermal synthesis of few-layered and edge-abundant MoS2/C nanocomposites with enhanced electrocatalytic performance for hydrogen evolution reaction [J]. Advanced Powder Technology, 2015, 26 (5): 1273–1280.

    [26] Baubet B, Devers E, Hugon A, et al. The influence of MoS2 slab 2D morphology and edge state on the properties of aluminasupported molybdenum sulfide catalysts [J]. Applied Catalysis A: General, 2014, 487 (10): 72–81.

    [27] Yin Z J, Zhao J, Wang B W, et al. Insight for the effect of bridging S22− in molybdenum sulfide catalysts toward sulfur-resistant methanation [J]. Applied Surface Science, 2019, 471 (12): 670–677.

    [28] Zhang H P, Lin H F, Zheng Y, et al. Understanding of the effect of synthesis temperature on the crystallization and activity of nano-MoS2 catalyst [J]. Applied Catalysis B: Environmental, 2015, 165 (4): 537–546.

    [29] Panpranot J, Kaewgun S, Praserthdam P. Metal–support interaction in mesoporous silica supported cobalt Fischer–Tropsch catalysts [J]. Reaction Kinetics and Catalysis Letters, 2005, 85 (2): 299–304.

    [30] Ting L R L, Deng Y L, Ma L, et al. Catalytic activities of sulfur atoms in amorphous molybdenum sulfide for the electrochemical hydrogen evolution reaction [J]. ACS Catalysis, 2016, 6 (2): 861–867.

    [31] Afanasiev P, Jobic H, Lorentz C, et al. Low-temperature hydrogen interaction with amorphous molybdenum sulfides MoSx [J]. Journal of Physical Chemistry C, 2009, 113 (10): 4136–4146.

This Article


CN: 11-1946/TQ

Vol 70, No. 10, Pages 3941-3948

October 2019


Article Outline


  • Introduction
  • 1 Experimental materials and methods
  • 2 Results and discussion
  • 3 Conclusions
  • Description of symbols
  • References