Research progress in active phase structure and reaction mechanism of MoS2-based catalysts for hydrodesulfurization

doi:10.16085/j.issn.1000-6613.2018-0324

Abstract

Abstract:

Hydrodesulfurization(HDS) is an important process in producing clean fuel. MoS₂-based catalysts are the major catalysts in HDS, therefore a thorough understanding of the active phase structure and HDS mechanism is useful for the development of new catalysts. This paper reviewed the active phase structure of MoS₂-based catalysts， including the effects of sulfiding conditions, promoter atoms and support type. And a general overview of the challenges of characterization on the active phase structure of MoS₂-based catalysts was provided. The microstructure characteristics of the active phase under different conditions were summarized. Meanwhile, the catalytic mechanism of thiophene HDS was analyzed based on the composition and structure of MoS₂-based catalysts, and the results indicated that the HDS activity was closely related to the catalyst’s microstructure. Finally, the important role of theoretical calculation in the development and design of efficient hydrodesulfurization catalysts was outlined.

Key words: hydrodesulfurization, catalyst, microstructure, catalysis, thiophene

摘要：

加氢脱硫工艺在清洁油品生产过程中发挥着重要作用，而MoS₂基催化剂是加氢脱硫的主要催化剂，因此对MoS₂基催化剂活性相和催化反应机理的深入研究有助于从原子层面上对催化剂进行优化设计。本文首先介绍了国内外有关MoS₂基催化剂活性相形貌结构的研究，着重探讨了硫化气氛、助剂和载体类型对活性相结构的影响，以及现有表征技术在MoS₂基催化剂活性相形貌结构研究中所面临的挑战，总结了不同条件下活性相的微观结构特征；同时，从MoS₂基催化剂的活性相组成和结构角度分析了噻吩的加氢脱硫机理，发现了加氢脱硫活性与催化剂微观结构之间的紧密联系；最后展望了理论计算在设计和开发高效加氢脱硫催化剂过程中的重要指导作用。

关键词: 加氢脱硫, 催化剂, 显微结构, 催化（作用）, 噻吩

CLC Number:

TQ426

Shuo LI, Yibin LIU, Xiang FENG, Chaohe YANG. Research progress in active phase structure and reaction mechanism of MoS₂-based catalysts for hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 867-875.

李硕, 刘熠斌, 冯翔, 杨朝合. MoS₂基催化剂加氢脱硫反应活性相和作用机理研究进展[J]. 化工进展, 2019, 38(02): 867-875.

Figures/Tables 10

References 63

1	LIU B , LIU L , WANG Z , et al . Effect of hydrogen spillover in selective hydrodesulfurization of FCC gasoline over the CoMo catalyst[J]. Catalysis Today, 2017, 282: 214-221．
2	LIU L H , LIU S Q , YIN H L , et al . Hydrogen spillover effect between Ni₂P and MoS₂ catalysts in hydrodesulfurization of dibenzothiophene[J]. Journal of Fuel Chemistry and Technology, 2015, 43(6): 708-713．
3	李大东 . 加氢处理工艺与工程[M]. 北京: 中国石化出版社, 2004: 93-94．
	LI D D . Hydrotreating technology and engineering[M]. Beijing: China Petrochemical Press, 2004: 93-94．
4	刘丽, 郭蓉, 孙进, 等．柴油加氢脱硫催化剂的研究进展[J]．化工进展, 2016, 35(11): 3503-3510．
	LIU L , GUO R , SUN J , et al . The research development of diesel hydrodesulfurization catalysts[J]. Chemical Industry and Engineering Progress, 2016, 35(11): 3503-3510．
5	王继元, 堵文斌, 陈韶辉, 等 . TiO₂载体在柴油加氢脱硫中的应用进展[J]. 化工进展, 2010, 29(4): 654-658．
	WANG J Y , DU W B , CHEN S H , et al . Progress in application of TiO₂ support for catalytic diesel hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2010, 29(4): 654-658．
6	刘迪, 张景成, 刘晨光．非负载型加氢精制催化剂的制备及工业应用研究进展[J]．化工进展, 2010, 29(4): 643-648．
	LIU D , ZHANG J C , LIU C G . Progress in preparation and industrial application of unsupported hydrotreating catalysts[J]. Chemical Industry and Engineering Progress, 2010, 29(4): 643-648．
7	仝建波, 蔺阳, 刘淑玲, 等 . 加氢脱硫催化剂载体的研究进展[J]. 化工进展, 2014, 33(5): 1170-1179．
	TONG J B , LIN Y , LIU S L , et al . Recent progress in the support of hydrodesulfurization catalysts[J]. Chemical Industry and Engineering Progress, 2014, 35(5): 1170-1179．
8	LIPSCH J M J G , SCHUIT G C A . The CoO MoO₃ Al₂O₃ catalyst: Ⅱ．The structure of the catalyst[J]. Journal of Catalysis, 1969, 15(2): 174-178．
9	VOORHOEVE R J H , STUIVER J C M . The mechanism of the hydrogenation of cyclohexene and benzene on nickel-tungsten sulfide catalysts[J]．Journal of Catalysis, 1971, 23(2): 243-252．
10	ASUA J M , DELMON B ．Separation of the kinetic terms in catalytic reactions with varying number of active sites (case of the remote control model)[J]. Applied Catalysis, 1984, 12(2): 249-262.
11	DAAGE M , CHIANELLI R R . Structure-function relations in molybdenum sulfide catalysts: the “Rim-Edge”model[J]. Journal of Catalysis, 1994, 149: 414-427.
12	TOPSOEE H , CLAUSEN B S , NAN Y T, et al . Recent basic research in hydrodesulfurization catalysis[J]. Industrial & Engineering Chemistry Fundamentals, 1986, 25(1): 25-36.
13	TOPSØE H , CLAUSEN B S , CANDIA R , et al . In situ Mössbauer emission spectroscopy studies of unsupported and supported sulfided CoMo hydrodesulfurization catalysts: evidence for and nature of a CoMoS phase[J]. Journal of Catalysis, 1981, 68(2): 433-452.
14	MAUGÉ F , DUCHET J C , LAVALLEY J C , et al . The sulphided state of nickel molybdenum catalysts supported on zirconia and aluminates[J]. Catalysis Today, 1991, 10(91): 561-577.
15	CALAIS C , MATSUBAYASHI N , GEANTET C , et al . Crystallite size determination of highly dispersed unsupported MoS₂ catalysts[J]. Journal of Catalysis, 1998, 174(2): 130-141.
16	SHIDO T , PRINS R . Why EXAFS underestimated the size of small supported MoS₂ particles[J]. The Journal of Physical Chemistry B, 1998, 102(43): 8426-8435.
17	KONG D S , WANG H T , CHA J J, et al . Synthesis of MoS₂ and MoSe₂ films with vertically aligned layers[J]. Nano Letters, 2013, 13(3): 1341-1347.
18	TOPSØE H , CLAUSEN B S , MASSOTH F E . Hydrotreating catalysis[M]. Berlin: Springer-Verlag, 1996.
19	DING S J , ZHOU Y S , WEI Q , et al . Substituent effects of 4,6-DMDBT on direct hydrodesulfurization routes catalyzed by Ni-Mo-S active nanocluster-A theoretical study[J]. Catalysis Today, 2018, 305: 28-39.
20	HAANDEL L V , BREMMER G M , HENSEN E J M , et al . Influence of sulfiding agent and pressure on structure and performance of CoMo/Al₂O₃ hydrodesulfurization catalysts[J]. Journal of Catalysis, 2016, 342: 27-39.
21	LAURITSEN J V , BOLLINGER M V , LÆGSGAARD E , et al . Atomic-scale insight into structure and morphology changes of MoS₂ nanoclusters in hydrotreating catalysts[J]. Journal of Catalysis, 2004, 221(2): 510-522.
22	LIU B , CHAI Y M , LI Y P , et al . Effect of sulfidation atmosphere on the performance of the CoMo/γ-Al₂O₃ catalysts in hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A: General, 2014, 471: 70-79.
23	RAYBAUD P , HAFNER J , KRESSE G , et al . Ab initio study of the H₂-H₂S/MoS₂ gas-solid interface: the nature of the catalytically active sites[J]. Journal of Catalysis, 2000, 189(1): 129-146.
24	SCHWEIGER H , RAYBAUD P , KRESSE G , et al . Shape and edge sites modifications of MoS₂ catalytic nanoparticles induced by working conditions: a theoretical study[J]. Journal of Catalysis, 2002, 207(1): 76-87.
25	MOSES P G , HINNEMANN B , TOPSØE H , et al . The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS₂ catalysts at realistic conditions: a density functional study[J]. Journal of Catalysis, 2007, 248(2): 188-203.
26	鞠雅娜, 兰玲, 刘坤红, 等 . 催化裂化汽油深度加氢脱硫催化剂的研制及性能评价[J]. 化工进展, 2017, 36(7): 2511-2516.
	JU Y N , LAN L , LIU K H , et al . Preparation and evaluation of a deep hydrodesulfurization(HDS) catalyst for catalytic cracking gasoline[J]. Chemical Industry and Engineering Progress, 2017, 36(7): 2511-2516.
27	KIBSGAARD J , TUXEN A , KNUDSEN K G , et al . Comparative atomic-scale analysis of promotional effects by late 3D-transition metals in MoS₂ hydrotreating catalysts[J]. Journal of Catalysis, 2010, 272(2): 195-203.
28	LAURITSEN J V , KIBSGAARD J , OLESEN G H , et al . Location and coordination of promoter atoms in Co- and Ni-promoted MoS₂-based hydrotreating catalysts[J]. Journal of Catalysis, 2007, 249(2): 220-233.
29	KREBS E , SILVI B , RAYBAUD P . Mixed sites and promoter segregation: a DFT study of the manifestation of Le Chatelier’s principle for the Co(Ni)MoS active phase in reaction conditions[J]. Catalysis Today, 2008, 130(1): 160-169.
30	BARA C , LAMIC-HUMBLOT A F , FONDA E , et al . Surface-dependent sulfidation and orientation of MoS₂ slabs on alumina-supported model hydrodesulfurization catalysts[J]. Journal of Catalysis, 2016, 344: 591-605.
31	LAURITSEN J V , JACOBSEN K W , NØRSKOV J K , et al . One-dimensional metallic edge states in MoS₂ [J]. Physical Review Letters, 2001, 87(19): 196803.
32	COSTA D , ARROUVEL C , BREYSSE M , et al . Edge wetting effects of γ Al₂O₃ and anatase-TiO₂ supports by MoS₂ and CoMoS active phases: a DFT study[J]. Journal of Catalysis, 2007, 246(2): 325-343.
33	WALTON A S , LAURITSEN J V , TOPSØE H , et al . MoS₂ nanoparticle morphologies in hydrodesulfurization catalysis studied by scanning tunneling microscopy[J]. Journal of Catalysis, 2013, 308: 306-318.
34	KIBSGAARD J , LAURITSEN J V , LÆGSGAARD E , et al . Cluster-support interactions and morphology of MoS₂ nanoclusters in a graphite-supported hydrotreating model catalyst[J]. Journal of the American Chemical Society, 2006, 128(42): 13950-13958.
35	KIBSGAARD J , CLAUSEN B S , TOPSØE H , et al . Scanning tunneling microscopy studies of TiO₂-supported hydrotreating catalysts: anisotropic particle shapes by edge-specific MoS₂-support bonding[J]. Journal of Catalysis, 2009, 263(1): 98-103.
36	LI Y , LI A T , LI F F , et al . Application of HF etching in a HRTEM study of supported MoS₂ catalysts[J]. Journal of Catalysis, 2014, 317: 240-252.
37	KOLBOE S . Catalytic hydrodesulfurization of thiophene: Ⅶ. Comparison between thiophene, tetrahydrothiophene, and n-butanethiol[J]. Canadian Journal of Chemistry, 1969, 47(2): 352-355.
38	AMBERG C H . Molybdenum in hydrodesulphurisation catalysts[J]. Journal of the Less Common Metals, 1974, 6(1/2): 339-352.
39	KRAUS J , ZDRAŽIL M . Tetrahydrothiophene as intermediate in the hydrodesulfurization of thiophene[J]. Reaction Kinetics and Catalysis Letters, 1977, 6(4): 475-480.
40	KIERAN P , KEMBALL C . Some catalytic reactions of thiophene on disulfides of tungsten and molybdenum[J]. Journal of Catalysis, 1965, 4(3): 394-402.
41	NØRSKOV J K , CLAUSEN B S , TOPSØE H . Understanding the trends in the hydrodesulfurization activity of the transition metal sulfides[J]. Catalysis Letters, 1992, 13(1): 1-8.
42	NAGAI M , SATO T , AIBA A . Poisoning effect of nitrogen compounds on dibenzothiophene hydrodesulfurization on sulfided NiMoAl₂O₃ catalysts and relation to gas-phase basicity[J]. Journal of Catalysis, 1986, 97(1): 52-58.
43	VOPA V L , SATTERFIELD C N . Poisoning of thiophene hydrodesulfurization by nitrogen compounds[J]. Journal of Catalysis, 1988, 110(2): 375-387.
44	RANGARAJAN S , MAVRIKAKIS M . DFT insights into the competitive adsorption of sulfur-and nitrogen-containing compounds and hydrocarbons on Co-promoted molybdenum sulfide catalysts[J]. ACS Catalysis, 2016, 6(5): 2904-2917.
45	PRINS R , EGOROVA M , RÖTHLISBERGER A , et al . Mechanisms of hydrodesulfurization and hydrodenitrogenation[J]. Catalysis Today, 2006, 111(1/2): 84-93.
46	EGOROVA M , PRINS R . Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over sulfided NiMo/γ Al₂O₃, CoMo/γ-Al₂O₃, and Mo/γ-Al₂O₃ catalysts[J]. Journal of Catalysis, 2004, 225(2): 417-427.
47	RANGARAJAN S , MAVRIKAKIS M . On the preferred active sites of promoted MoS₂ for hydrodesulfurization with minimal organonitrogen inhibition[J]. ACS Catalysis, 2016, 7(1): 501-509.
48	LAURITSEN J V , NYBERG M , VANG R T . Chemistry of one-dimensional metallic edge states in MoS₂ nanoclusters[J]. Nanotechnology, 2003, 14(3): 385.
49	LAURITSEN J V , NYBERG M , NØRSKOV J K , et al . Hydrodesulfurization reaction pathways on MoS₂ nanoclusters revealed by scanning tunneling microscopy[J]. Journal of Catalysis, 2004, 224(1): 94-106.
50	SULLIVAN D L , EKERDT J G . Mechanisms of thiophene hydrodesulfurization on model molybdenum catalysts[J]. Journal of Catalysis, 1998, 178(1): 226-233.
51	LIU B , ZHAO Z , WANG D X , et al . A theoretical study on the mechanism for thiophene hydrodesulfurization over zeolite L-supported sulfided Co-Mo catalysts: insight into the hydrodesulfurization over zeolite-based catalysts[J]. Computational & Theoretical Chemistry, 2015, 1052: 47-57.
52	MARKEL E J , SCHRADER G L , SAUER N N , et al . Thiophene, 2,3- and 2,5-dihydrothiophene and tetrahydrothiophene hydrodesulfurization on Mo and Re γ Al₂O₃ catalysts[J]. Journal of Catalysis, 1989, 116(1): 11-22.
53	BORGNA A , HENSEN E J M , COULIER L , et al . Intrinsic thiophene hydrodesulfurization kinetics of a sulfided NiMo/SiO₂ model catalyst: volcano-type behavior[J]. Catalysis Letters, 2003, 90(3): 117-122.
54	VRINAT M L . The kinetics of the hydrodesulfurization process - a review[J]. Applied Catalysis, 1983, 6(2): 137-158.
55	SCHULZ H , DO D . Fast and slow steps of hydrodesulfurization[J]. Bulletin des Sociétés Chimiques Belges, 1984, 93(8/9): 645-652.
56	MOSES P G , HINNEMANN B , TOPSØE H , et al . Corrigendum to“The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS₂ catalysts at realistic conditions: a density functional study” [Journal of Catalysis, 2007, 248: 188][J]. Journal of Catalysis, 2008, 260(1): 202-203.
57	MOSES P G , HINNEMANN B , TOPSØE H , et al . The effect of Co-promotion on MoS₂ catalysts for hydrodesulfurization of thiophene: a density functional study[J]. Journal of Catalysis, 2009, 268(2): 201-208.
58	GRØNBORG S S , ŠARIĆ M , MOSES P G , et al . Atomic scale analysis of sterical effects in the adsorption of 4, 6-dimethyldibenzothiophene on a CoMoS hydrotreating catalyst[J]. Journal of Catalysis, 2016, 344: 121-128.
59	ZHENG P , DUAN A J , CHI K B , et al . Influence of sulfur vacancy on thiophene hydrodesulfurization mechanism at different MoS₂ edges: a DFT study[J]. Chemical Engineering Science, 2017, 164: 292-306.
60	DING S J , JIANG S J , ZHOU Y S , et al . Catalytic characteristics of active corner sites in CoMoS nanostructure hydrodesulfurization-a mechanism study based on DFT calculations[J]. Journal of Catalysis, 2017, 345: 24-38.
61	CHEN J J , MAUGÉ F , FALLAH J E , et al . IR spectroscopy evidence of MoS₂, morphology change by citric acid addition on MoS₂/Al₂O₃ catalysts-a step forward to differentiate the reactivity of M-edge and S-edge[J]. Journal of Catalysis, 2014, 320(1): 170-179.
62	HUANG T T , XU J D , FAN Y . Effects of concentration and microstructure of active phases on the selective hydrodesulfurization performance of sulfided CoMo/Al₂O₃ catalysts[J]. Applied Catalysis B: Environmental, 2017, 220: 42-56.
63	LI P , CHEN Y D , ZHANG C , et al . Highly selective hydrodesulfurization of gasoline on unsupported Co-Mo sulfide catalysts: effect of MoS₂ morphology[J]. Applied Catalysis A: General, 2017, 533: 99-108.

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Research progress in active phase structure and reaction mechanism of MoS₂-based catalysts for hydrodesulfurization

MoS₂基催化剂加氢脱硫反应活性相和作用机理研究进展

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