CO耐硫甲烷化MoS<sub>2</sub>/Si-ZrO<sub>2</sub>催化剂的失活原因研究

顾佳; 辛忠; 高文莉; 何璐铭; 赵瑞

doi:10.11949/0438-1157.20190565

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CO耐硫甲烷化MoS₂/Si-ZrO₂催化剂的失活原因研究

催化、动力学与反应器 | 更新时间：2026-07-24

- CO耐硫甲烷化MoS₂/Si-ZrO₂催化剂的失活原因研究
- Deactivation behaviors of MoS₂/Si-ZrO₂ catalyst during sulfur-resistant CO methanation
- 化工学报 2019年70卷第10期页码：3941-3948
- 作者机构：
  
  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
- 作者简介：
  
  顾佳（1991—），女，博士研究生，gujia_1991@163.com
  辛忠（1962—），男，博士，教授，xzh@ecust.edu.cn
- 基金信息：
  
  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)
- DOI：10.11949/0438-1157.20190565
  中图分类号： TQ 546.4
- 收稿：2019-05-24，
  
  修回：2019-07-21，
  
  网络首发：2026-07-24，
  
  纸质出版：2019-10-05
- 稿件说明：
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顾佳, 辛忠, 高文莉, 何璐铭, 赵瑞. CO耐硫甲烷化MoS₂/Si-ZrO₂催化剂的失活原因研究[J]. 化工学报, 2019, 70(10): 3941-3948 DOI: 10.11949/0438-1157.20190565.

GU Jia, XIN Zhong, GAO Wenli, HE Luming, ZHAO Rui. Deactivation behaviors of MoS₂/Si-ZrO₂ catalyst during sulfur-resistant CO methanation[J]. CIESC Journal, 2019, 70(10): 3941-3948 DOI: 10.11949/0438-1157.20190565.
顾佳, 辛忠, 高文莉, 何璐铭, 赵瑞. CO耐硫甲烷化MoS₂/Si-ZrO₂催化剂的失活原因研究[J]. 化工学报, 2019, 70(10): 3941-3948 DOI: 10.11949/0438-1157.20190565. DOI：

GU Jia, XIN Zhong, GAO Wenli, HE Luming, ZHAO Rui. Deactivation behaviors of MoS₂/Si-ZrO₂ catalyst during sulfur-resistant CO methanation[J]. CIESC Journal, 2019, 70(10): 3941-3948 DOI: 10.11949/0438-1157.20190565. DOI：

摘要

采用等体积浸渍法制备MoS

/Si-ZrO

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2H

∶2CO∶1N

（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(H

-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

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113938879&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113938842&type=

4.40266657

3.47133350

物种转变为S

物种和H

S。

Abstract

The MoS

/Si-ZrO

catalyst was prepared by an equal volume impregnation method

and the catalytic activity stability of CO for sulfur-tolerant methanation was evaluated. The CO conversion of the MoS

/Si-ZrO

catalyst decreased by 11% under the following condition: molar ratio of feed gas composition was 2H

∶2CO∶1N

; concentration of H

S was 0.01%; weight hourly space velocity was 6000 ml/(g·h); reaction temperature was 450℃ and reaction pressure was 2.5 MPa. The catalysts were further characterized by hydrogen temperature programmed reduction (H

-TPR)

X-rays photoelectron spectroscopy (XPS)

high-resolution transmission electron microscopy (HRTEM)

Raman spectra (RS)

inductively coupled plasma emission spectra (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 MoS

slabs grew longer and stacked more layers after long-term reaction and then covered the active sites. The root deactivation cause was attributed to parts of catalytic active bridging

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113938855&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113938864&type=

4.82599974

4.06400013

species converting to less active S

species and H

which resulted in the loss of active sites and sulfur element.

关键词

Keywords

references

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

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 .

Zhang X , Rui N , Jia X , et al . Effect of decomposition of catalyst prec ursor on Ni/CeO 2 activity for CO methanation [J ] . Chinese Journal of Catalysis , 2019 , 40 ( 4 ): 495 - 503 .

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 .

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 .

Andersson R , Boutonnet M , Järås S . Higher alcohols from syngas using a K/Ni/MoS 2 catalyst: trace sulfur in the product and effect of H 2 S-containing feed [J ] . Fuel , 2014 , 115 ( 1 ): 544 - 550 .

Shi G , Han W , Yuan P , et al . Sulfided Mo/Al 2 O 3 hydrodesulfurization catalyst prepared by ethanol-assisted chemical deposition method [J ] . Chinese Journal of Catalysis , 2013 , 34 ( 4 ): 659 - 666 .

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 .

Li M , Wang D , Li J , et al . Surfactant-assisted hydrothermally synthesized MoS 2 samples with controllable morphologies and structures for anthracene hydrogenation [J ] . Chinese Journal of Catalysis , 2017 , 38 ( 3 ): 597 - 606 .

Wang B , Yu W , Wang W , et al . Effect of boron addition on the MoO 3 /CeO 2 –Al 2 O 3 catalyst in the sulfur-resistant methanation [J ] . Chinese Journal of Chemical Engineering , 2018 , 26 ( 3 ): 509 - 513 .

Mortensen P M , Gardini D , Damsgaard C D , et al . Deactivation of Ni-MoS 2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol [J ] . Applied Catalysis A: General , 2016 , 523 ( 8 ): 159 - 170 .

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

Vogelaar B M , Steiner P , van Langeveld A D , et al . Deactivation of Mo/Al 2 O 3 and NiMo/Al 2 O 3 catalysts during hydrodesulfurization of thiophene [J ] . Applied Catalysis A: General , 2003 , 251 ( 1 ): 85 - 92 .

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 .

Li Z , He J , Wang H , et al . Enhanced methanation stability of nano-sized MoS 2 catalysts by adding Al 2 O 3 [J ] . Frontiers of Chemical Science and Engineering , 2016 , 9 ( 1 ): 33 - 39 .

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

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 .

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 .

Gu J , Xin Z , Tao M , et al . Effect of Si-modified zirconia on the properties of MoO 3 /Si-ZrO 2 catalysts for sulfur-resistant CO methanation [J ] . Applied Catalysis A: General , 2019 , 575 ( 4 ): 230 - 237 .

Gu J , Xin Z , Tao M , et al . Effect of reflux digestion time on MoO 3 /ZrO 2 catalyst for sulfur-resistant CO methanation [J ] . Fuel , 2019 , 241 ( 4 ): 129 - 137 .

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 .

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 .

He M , Kong F , Yin G , et al . Enhanced hydrogen evolution reaction activity of hydrogen-annealed vertical MoS 2 nanosheets [J ] . RSC Advances , 2018 , 8 ( 26 ): 14369 - 14376 .

Paul K K , Sreekanth N , Biroju R K , et al . Strongly enhanced visible light photoelectrocatalytic hydrogen evolution reaction in an n-doped MoS 2 /TiO 2 (B) heterojunction by selective decoration of platinum nanoparticles at the MoS 2 edge sites [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 45 ): 22681 - 22696 .

Ma L , Zhou X P , Xu X Y , et al . One-step hydrothermal synthesis of few-layered and edge-abundant MoS 2 /C nanocomposites with enhanced electrocatalytic performance for hydrogen evolution reaction [J ] . Advanced Powder Technology , 2015 , 26 ( 5 ): 1273 - 1280 .

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

Yin Z J , Zhao J , Wang B W , et al . Insight for the effect of bridging S 2 2- in molybdenum sulfide catalysts toward sulfur-resistant methanation [J ] . Applied Surface Science , 2019 , 471 ( 12 ): 670 - 677 .

Zhang H P , Lin H F , Zheng Y , et al . Understanding of the effect of synthesis temperature on the crystallization and activity of nano-MoS 2 catalyst [J ] . Applied Catalysis B: Environmental , 2015 , 165 ( 4 ): 537 - 546 .

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 .

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 .

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 .

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CO耐硫甲烷化MoS2/Si-ZrO2催化剂的失活原因研究

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

DOI：10.11949/0438-1157.20190565

摘要

Abstract

关键词

Keywords

references

CO耐硫甲烷化MoS₂/Si-ZrO₂催化剂的失活原因研究

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