Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS<sub>2</sub> catalysts

LIU Juan; LI Wen-ying; FENG Jie; GAO Xiang

doi:10.1016/S1872-5813(21)60105-6

Volume 49 Issue 10

Oct. 2021

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2021 > 49(10): 1513-1521

LIU Juan, LI Wen-ying, FENG Jie, GAO Xiang. Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS2 catalysts[J]. Journal of Fuel Chemistry and Technology, 2021, 49(10): 1513-1521. doi: 10.1016/S1872-5813(21)60105-6

Citation:

LIU Juan, LI Wen-ying, FENG Jie, GAO Xiang. Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS₂ catalysts[J]. Journal of Fuel Chemistry and Technology, 2021, 49(10): 1513-1521. doi: 10.1016/S1872-5813(21)60105-6

Citation:

PDF( 1087 KB)

Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS₂ catalysts

doi: 10.1016/S1872-5813(21)60105-6

LIU Juan^{1, 2
,},
LI Wen-ying^{1
,
,},
FENG Jie¹,
GAO Xiang²

1.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
2.
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Funds: The project was supported by National Natural Science Foundation of China (22038008) and National Key Research and Development Plan Projects of China (2016YFB0600305)

Received Date: 2021-02-23
Rev Recd Date: 2021-04-30

Available Online: 2021-06-03

Publish Date: 2021-10-30

Abstract

Abstract

To obtain type II active phase with higher activity, MoS₂-based catalysts were prepared by thermal decomposition of ammonium tetrathiomolybdate. The influence of Ni adding way and decomposition atmosphere on the microstructures of MoS₂ slabs, chemical state of surface elements, as well as hydrodesulfurization and hydrodenitrogenation activities were investigated. Results indicated that simultaneous impregnation of Mo and Ni precursors caused in situ deposition of amorphous NiMoS₄ over the support surface, which subsequently facilitated the substitution of Mo atoms by Ni atoms at MoS₂ edges. Accordingly, these decorated catalysts exhibited higher dispersion of MoS₂ slabs with more suitable slab length (3–5 nm) and stacking number (2–4), which attributed to larger numbers of rim and corner active sites exposed at the edges. These active sites were essential in hydrogenation and hydrogenolysis reactions. In comparison with N₂ atmosphere, thermal decomposition in H₂ atmosphere was more conducive to the substitution of Mo atoms by Ni atoms at MoS₂ edges, which provided more active Ni-Mo-S structures for the adsorption, activation and hydrogenolysis of quinoline and dibenzothiophene molecules. The catalyst prepared by thermal decomposition of NiMoS₄ in H₂ atmosphere showed superior activities in the quinoline hydrodenitrogenation with 23.8% conversion and in the dibenzothiophene hydrodesulfurization with 93.3% conversion, under the conditions of 340 °C, 3 MPa, a weight hourly space velocity of 23.4 h^–1, H₂/oil volume ratio of 600 and 0.1 g of NMS-H₂ catalysts.
- NiMo sulfide,
- quinoline,
- dibenzothiophene,
- hydrogenation reaction

FullText(HTML)

References(39)

References

[1]	刘敏, 陈贵锋, 王永刚, 赵鹏, 曲思建. 白石湖煤液化粗油加氢精制过程硫、氮化合物转化规律[J]. 燃料化学学报,2019,47(7):870−875. doi: 10.3969/j.issn.0253-2409.2019.07.012 LIU Min, CHEN Gui-feng, WANG Yong-gang, ZHAO Peng, QU Si-jian. Conversion of sulphur and nitrogen compounds in hydrofining process of Baishihu coal liquefaction oil[J]. J Fuel Chem Technol,2019,47(7):870−875. doi: 10.3969/j.issn.0253-2409.2019.07.012
[2]	VÁZQUEZ-GARRIDO I, LÓPEZ-BENÍTEZ A, BERHAULT G, GUEVARA-LARA A. Effect of support on the acidity of NiMo/Al₂O₃-MgO and NiMo/TiO₂-Al₂O₃ catalysts and on the resulting competitive hydrodesulfurization/hydrodenitrogenation reactions[J]. Fuel,2019,236:55−64. doi: 10.1016/j.fuel.2018.08.053
[3]	LIU Z, HAN W, HU D, SUN S, HU A, WANG Z, JIA Y, ZHAO X, YANG Q. Effects of Ni-Al₂O₃ interaction on NiMo/Al₂O₃ hydrodesulfurization catalysts[J]. J Catal,2020,387:62−72. doi: 10.1016/j.jcat.2020.04.008
[4]	EIJSBOUTS S, LI X, JUAN-ALCANIZ J, VAN DEN OETELAAR L C A, BERGWERFF J A, LOOS J, CARLSSON A, VOGT E T C. Electron tomography reveals the active phase-support interaction in sulfidic hydroprocessing catalysts[J]. ACS Catal,2017,7(7):4817−4821. doi: 10.1021/acscatal.7b01201
[5]	GUTIÉRREZ O Y, KLIMOVA T. Effect of the support on the high activity of the (Ni)Mo/ZrO₂-SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4, 6-DMDBT[J]. J Catal,2011,281(1):50−62. doi: 10.1016/j.jcat.2011.04.001
[6]	GE H, WEN X-D, RAMOS M A, CHIANELLI R R, WANG S, WANG J, QIN Z, LYU Z, LI X. Carbonization of ethylenediamine coimpregnated CoMo/Al₂O₃ catalysts sulfided by organic sulfiding agent[J]. ACS Catal,2014,4(8):2556−2565. doi: 10.1021/cs500477x
[7]	BARA C, LAMIC-HUMBLOT A-F, FONDA E, GAY A-S, TALEB A-L, DEVERS E, DIGNE M, PIRNGRUBER G D, CARRIER X. Surface-dependent sulfidation and orientation of MoS₂ slabs on alumina-supported model hydrodesulfurization catalysts[J]. J Catal,2016,344:591−605. doi: 10.1016/j.jcat.2016.10.001
[8]	BOUWENS S M A M, VANZON F B M, VANDIJK M P, VANDERKRAAN A M, DEBEER V H J, VANVEEN J A R, KONINGSBERGER D C. On the structural differences between alumina-supported CoMoS type I and alumina-, silica-, and carbon-supported CoMoS type II phases studied by XAFS, MES, and XPS[J]. J Catal,1994,146(2):375−393. doi: 10.1006/jcat.1994.1076
[9]	OKAMOTO Y, KATO A, USMAN, RINALDI N, FUJIKAWA T, KOSHIKA H, HIROMITSU I, KUBOTA T. Effect of sulfidation temperature on the intrinsic activity of Co-MoS₂ and Co-WS₂ hydrodesulfurization catalysts[J]. J Catal,2009,265(2):216−228. doi: 10.1016/j.jcat.2009.05.003
[10]	SÁNCHEZ J, MORENO A, MONDRAGÓN F, SMITH K J. Morphological and structural properties of MoS₂ and MoS₂-amorphous silica-alumina dispersed catalysts for slurry-phase hydroconversion[J]. Energy Fuels,2018,32(6):7066−7077. doi: 10.1021/acs.energyfuels.8b01081
[11]	MELLO M D D, BRAGGIO F D A, MAGALHÃES B D C, ZOTIN J L, SILVA M A P D. Effects of phosphorus content on simultaneous ultradeep HDS and HDN reactions over NiMoP/alumina catalysts[J]. Ind Eng Chem Res,2017,56(37):10287−10299. doi: 10.1021/acs.iecr.7b02718
[12]	BADOGA S, DALAI A K, ADJAYE J, HU Y. Insights into individual and combined effects of phosphorus and EDTA on performance of NiMo/MesoAl₂O₃ catalyst for hydrotreating of heavy gas oil[J]. Fuel Process Technol,2017,159:232−246. doi: 10.1016/j.fuproc.2017.01.034
[13]	王广建, 赵强, 陈国良, 王建爽, 石林. 柠檬酸引入方式对CoMo/TiO₂-Al₂O₃催化剂加氢脱硫性能的影响[J]. 工业催化,2019,27(7):54−60. doi: 10.3969/j.issn.1008-1143.2019.07.010 WANG Guang-jian, ZHAO Qiang, CHEN Guo-liang, WANG Jian-shuang, SHI Lin. Effect of citric acid introduction methods on hydrodesulfurization performance of CoMo/TiO₂-Al₂O₃ catalysts[J]. Ind Catal,2019,27(7):54−60. doi: 10.3969/j.issn.1008-1143.2019.07.010
[14]	SOLNICKOVA L. Nano-sized carbon-supported molybdenum disulphide particles for hydrodesulphurization[D]. Vancouver: The University of British Columbia, 2016.
[15]	GANIYU S A, ALHOOSHANI K, ALI S A. Single-pot synthesis of Ti-SBA-15-NiMo hydrodesulfurization catalysts: Role of calcination temperature on dispersion and activity[J]. Appl Catal B: Environ,2017,203:428−441. doi: 10.1016/j.apcatb.2016.10.052
[16]	VARAKIN A N, MOZHAEV A V, PIMERZIN A A, NIKULSHIN P A. Comparable investigation of unsupported MoS₂ hydrodesulfurization catalysts prepared by different techniques: Advantages of support leaching method[J]. Appl Catal B: Environ,2018,238:498−508. doi: 10.1016/j.apcatb.2018.04.003
[17]	NIEFIND F, BENSCH W, DENG M, KIENLE L, CRUZ-REYES J, GRANADOS J M D V. Co-promoted MoS₂ for hydrodesulfurization: New preparation method of MoS₂ at room temperature and observation of massive differences of the selectivity depending on the activation atmosphere[J]. Appl Catal A: Gen,2015,497:72−84. doi: 10.1016/j.apcata.2015.03.003
[18]	SUN K, GUO H, JIAO F, CHAI Y, LI Y, LIU B, MINTOVA S, LIU C. Design of an intercalated Nano-MoS₂ hydrophobic catalyst with high rim sites to improve the hydrogenation selectivity in hydrodesulfurization reaction[J]. Appl Catal B: Environ,2021,286:119907. doi: 10.1016/j.apcatb.2021.119907
[19]	LIU B, LIU L, CHAI Y, ZHAO J, LI Y, LIU D, LIU Y, LIU C. Effect of sulfiding conditions on the hydrodesulfurization performance of the ex-situ presulfided CoMoS/γ-Al₂O₃ catalysts[J]. Fuel,2018,234:1144−1153. doi: 10.1016/j.fuel.2018.08.001
[20]	LAI W, CHEN Z, ZHU J, YANG L, ZHENG J, YI X, FANG W. NiMoS flower-like structure with self-assembled nanosheets as high-performance hydrodesulfurization catalysts[J]. Nanoscale,2016,8(6):3823−3833. doi: 10.1039/C5NR08841K
[21]	PELARDY F, SANTOS A S, DAUDIN A, DEVERS E, BELIN T, BRUNET S. Sensitivity of supported MoS₂-based catalysts to carbon monoxide for selective HDS of FCC gasoline: Effect of nickel or cobalt as promoter[J]. Appl Catal B: Environ,2017,206:24−34. doi: 10.1016/j.apcatb.2016.12.057
[22]	BREMMER G M, HAANDEL L, HENSEN E J M, FRENKEN J W M, KOOYMAN P J. The effect of oxidation and resulfidation on (Ni/Co)MoS₂ hydrodesulfurisation catalysts[J]. Appl Catal B: Environ,2019,243:145−150. doi: 10.1016/j.apcatb.2018.10.014
[23]	RANGARAJAN S, MAVRIKAKIS M. On the preferred active sites of promoted MoS₂ for hydrodesulfurization with minimal organonitrogen inhibition[J]. ACS Catal,2017,7(1):501−509. doi: 10.1021/acscatal.6b02735
[24]	BERHAULT G, MEHTA A, PAVEL A C, YANG J, RENDON L, YÁCAMAN M J, ARAIZA L C, MOLLER A D, CHIANELLI R R. The role of structural carbon in transition metal sulfides hydrotreating catalysts[J]. J Catal,2001,498:9−19.
[25]	LIU J, LI W-Y, FENG J, GAO X, LUO Z-Y. Promotional effect of TiO₂ on quinoline hydrodenitrogenation activity over Pt/γ-Al₂O₃ catalysts[J]. Chem Eng Sci,2019,207:1085−1095. doi: 10.1016/j.ces.2019.07.040
[26]	LIU J, LI W-Y, FENG J, GAO X. Effects of Fe species on promoting the dibenzothiophene hydrodesulfurization over the Pt/γ-Al₂O₃ catalysts[J]. Catal Today,2020,. doi: 10.1016/j.cattod.2020.07.035
[27]	DAAGE M, CHIANELLI R R. Structure-function relations in molybdenum sulfide catalysts: The "Rim-Edge" model[J]. J Catal,1994,149(2):414−427. doi: 10.1006/jcat.1994.1308
[28]	KASZTELAN S, TOULHOAT H, GRIMBLOT J, BONNELLE J P. A geometrical model of the active phase of hydrotreating catalysts[J]. Appl Catal,1984,13(1):127−159. doi: 10.1016/S0166-9834(00)83333-3
[29]	XU J, GUO Y, HUANG T, FAN Y. Hexamethonium bromide-assisted synthesis of CoMo/graphene catalysts for selective hydrodesulfurization[J]. Appl Catal B: Environ,2019,244:385−395. doi: 10.1016/j.apcatb.2018.11.065
[30]	ZHOU W, ZHANG Q, ZHOU Y, WEI Q, DU L, DING S, JIANG S, ZHANG Y. Effects of Ga- and P-modified USY-based NiMoS catalysts on ultra-deep hydrodesulfurization for FCC diesels[J]. Catal Today,2018,305:171−181. doi: 10.1016/j.cattod.2017.07.006
[31]	JIAO J, FU J, WEI Y, ZHAO Z, DUAN A, XU C, LI J, SONG H, ZHENG P, WANG X, YANG Y, LIU Y. Al-modified dendritic mesoporous silica nanospheres-supported NiMo catalysts for the hydrodesulfurization of dibenzothiophene: Efficient accessibility of active sites and suitable metal-support interaction[J]. J Catal,2017,356:269−282. doi: 10.1016/j.jcat.2017.10.003
[32]	HU C, CREASER D, FOULADVAND S, GRÖNBECK H, SKOGLUNDH M. Methyl crotonate hydrogenation over Pt: Effects of support and metal dispersion[J]. Appl Catal A: Gen,2016,511:106−116. doi: 10.1016/j.apcata.2015.12.003
[33]	ALBERSBERGER S, SHI H, WAGENHOFER M, HAN J, GUTIÉRREZ O Y, LERCHER J A. On the enhanced catalytic activity of acid-treated, trimetallic Ni-Mo-W sulfides for quinoline hydrodenitrogenation[J]. J Catal,2019,380:332−342. doi: 10.1016/j.jcat.2019.09.034
[34]	NGUYEN M-T, TAYAKOUT-FAYOLLE M, CHAINET F, PIRNGRUBER G D, GEANTET C. Use of kinetic modeling for investigating support acidity effects of NiMo sulfide catalysts on quinoline hydrodenitrogenation[J]. Appl Catal A: Gen,2017,530:132−144. doi: 10.1016/j.apcata.2016.11.015
[35]	WANG H, LIU S, SMITH K J. Understanding selectivity changes during hydrodesulfurization of dibenzothiophene on Mo₂C/carbon catalysts[J]. J Catal,2019,369:427−439. doi: 10.1016/j.jcat.2018.11.035
[36]	RYDBERG H, DION M, JACOBSON N, SCHRÖDER E, HYLDGAARD P, SIMAK S, LANGRETH D, LUNDQVIST B. Van der waals density functional for layered structures[J]. Phys Rev Lett,2003,91(12):126402. doi: 10.1103/PhysRevLett.91.126402
[37]	BYSKOV L, NØRSKOV J, CLAUSEN B, TOPSØE H. DFT calculations of unpromoted and promoted MoS₂-based hydrodesulfurization catalysts[J]. J Catal,1999,187(1):109−122. doi: 10.1006/jcat.1999.2598
[38]	ZHENG P, LI T, CHI K, XIAO C, FAN J, WANG X, DUAN A. DFT insights into the formation of sulfur vacancies over corner/edge site of Co/Ni-promoted MoS₂ and WS₂ under the hydrodesulfurization conditions[J]. Appl Catal B: Environ,2019,257:117937. doi: 10.1016/j.apcatb.2019.117937
[39]	GUTIÉRREZ O, HRABAR A, HEIN J, YU Y, HAN J, LERCHER J. Ring opening of 1, 2, 3, 4-tetrahydroquinoline and decahydroquinoline on MoS₂/γ-Al₂O₃ and Ni-MoS₂/γ-Al₂O₃[J]. J Catal,2012,295:155−168. doi: 10.1016/j.jcat.2012.08.003