Hydrogen spillover effect between Ni<sub>2</sub>P and MoS<sub>2</sub> catalysts in hydrodesulfurization of dibenzothiophene

LIU Li-hua; LIU Shu-qun; YIN Hai-liang; LIU Yun-qi; LIU Chen-guang

Volume 43 Issue 06

Jun. 2015

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2015 > 43(06): 708-713

LIU Li-hua, LIU Shu-qun, YIN Hai-liang, LIU Yun-qi, LIU Chen-guang. Hydrogen spillover effect between Ni2P and MoS2 catalysts in hydrodesulfurization of dibenzothiophene[J]. Journal of Fuel Chemistry and Technology, 2015, 43(06): 708-713.

Citation:

LIU Li-hua, LIU Shu-qun, YIN Hai-liang, LIU Yun-qi, LIU Chen-guang. Hydrogen spillover effect between Ni₂P and MoS₂ catalysts in hydrodesulfurization of dibenzothiophene[J]. Journal of Fuel Chemistry and Technology, 2015, 43(06): 708-713.

Citation:

PDF( 2730 KB)

Hydrogen spillover effect between Ni₂P and MoS₂ catalysts in hydrodesulfurization of dibenzothiophene

1.
School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China;
2.
Academy of Science & Technology, China University of Petroleum, Dongying 257061, China;
3.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266555, China

Funds: Supported by the National Natural Science Foundation of China (21206197), the Natural Science Foundation of Anhui Province (1408085QB44), the Science-Technology Foundation for Fostering Talents of Huaibei City (20140316), the Youth Foundation of Huaibei Normal University (2013xqz01),and Promotive Research Fund for Excellent Young and Middle-aged Scientists of Shandong Province (BS2013CL021).

Received Date: 2015-03-20
Rev Recd Date: 2015-05-04
Publish Date: 2015-06-30

Abstract

Abstract

The hydrodesulfurization of dibenzothiophene over physically separated Ni₂P//MoS₂ catalyst beds was investigated.The results indicated that the hydrogen spillover effect appears between the Ni₂P/Al₂O₃ and MoS₂/Al₂O₃ catalysts in the hydrodesulfurization reaction, which can significantly enhance the concentration of active sites and the hydrodesulfurization rate over the MoS₂ catalyst. The spillover factor on Ni₂P//MoS₂is slightly higher than that on NiS_x//MoS₂, due to the higher hydrogen dissociation activity of Ni₂P; as a result, Ni₂P is a superior promoter to NiS_x for the MoS₂ catalyst.
- Ni₂P,
- MoS₂,
- hydrodesulfurization,
- hydrogen spillover effect,
- dibenzothiophene

FullText(HTML)

References(35)

References

SONG C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J]. Catal Today, 2003, 86(1/4): 211-263.

STANISLAUS A, MARAFI A, RANA M S. Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production[J]. Catal Today, 2010, 153(1/2): 1-68.

TOPSØE H, CLAUSEN B S, TOPSØE N Y, ZEUTHEN P. Progress in the design of hydrotreating catalysts based on fundamental molecular insight[J]. Stud Surf Sci Catal, 1989, 53: 77-102.

TOPSØE H, CLAUSEN B S. Importance of Co-Mo-S type structures in hydrodesulfuriza-tion[J]. Catal Rev Sci Eng, 1984, 26(3/4): 395-420.

KARROUA M, MATRALIS H, GRANGE P, DELMON B. Synergy between "NiMoS" and Co₉S₈ in the hydrogenation of cyclohexene and hydrodesulfurization of thiophene[J]. J Catal, 1993, 139(2): 371-374.

DELMON B. Are solid catalysts successfully emulating enzymes[J]? Chin J Catal, 2010, 26(8): 859-871.

TOPSØE H, CLAUSEN B S. Active sites and support effects in hydrodesulfurization catalysts[J]. Appl Catal, 1986, 25(1/2): 273-293.

TOPSØE H, HINNEMANN B, NØRSKOV J K, LAURITSEN J V, BESENBACHER F, HANSEN P L, HYTOFT G, EGEBERG R G, KNUDSEN K G. The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts[J]. Catal Today, 2005, 107-108: 12-22.

LAURITSEN J V, KIBSGAARD J, OLESEN G H, MOSES P G, HINNEMANN B, HELVEG S, NØRSKOV J K, CLAUSEN B S, TOPSØE H, LØGSGAARD E, BESENBACHER F. Location and coordination of promoter atoms in Co- and Ni-promoted MoS₂-based hydrotreating catalysts[J]. J Catal, 2007, 249(2): 220-233.

LAURITSEN J V, HELVEG S, LGSGAARD E, STENSGAARD I, CLAUSEN B S, TOPSØE H, BESENBACHER F. Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts[J]. J Catal, 2001, 197(1): 1-5.

KIBSGAARD J, LAURITSEN J V, GSGAARD E, CLAUSEN B S, TOPSØE H, BESENBACHER F. Cluster-support interactions and morphology of MoS₂ nanoclusters in a graphite-supported hydrotreating model catalyst[J]. J Am Chem Soc, 2006, 128(42): 13950-13958.

ESCALONA N, GARCIA R, LAGOS G, NAVARRETE C, BAEZA P, GIL-LLAMBIAS F J. Effect of the hydrogen spillover on the selectivity of dibenzothiophene hydrodesulfurization over CoS_x/γ-Al₂O₃, NiS_x/γ-Al₂O₃ and MoS₂/γ-Al₂O₃ catalysts[J]. Catal Commun, 2006, 7(12): 1053-1056.

BAEZA P, URETA-ZAÑARTU M S, ESCALONA N, OJEDA J, GIL-LLAMBIAS F J, DELMON B. Migration of surface species on supports: A proof of their role on the synergism between CoS_x or NiS_x and MoS₂ in HDS[J]. Appl Catal A: Gen, 2004, 274(1/2): 303-309.

OJEDA J, ESCALONA N, BAEZA P, ESCUDEY M, GIL-LLAMBIAS F J. Synergy between Mo/SiO₂ and Co/SiO₂ beds in HDS: A remote control effect[J]? Chem Commun, 2003, (13): 1608-1609.

VILLARROEL M, BAEZA P, ESCALONA N, OJEDA J, DELMON B, GIL-LLAMBIAS F J. MD//Mo and MD//W promotion via spillover hydrogen in hydrodesulfurization[J]. Appl Catal A: Gen, 2008, 345(2): 152-157.

BAEZA P, VILLARROEL M, ÁVILA P, LÓPEZ AGUDO A, DELMON B, GIL-LLAMBIAS F J. Spillover hydrogen mobility during Co-Mo catalyzed HDS in industrial-like conditions[J]. Appl Catal A: Gen, 2006, 304: 109-115.

VILLARROEL M, M NDEZ A, ÁGUILA G, ESCALONA N, BAEZA P, GIL-LLAMBIAS F. Synergism in alumina-supported noble metals and molybdenum stacked-bed catalysts via spillover hydrogen in gas-oil hydrodesulphurization[J]. Catal Today, 2010, 156(1/2): 65-68.

VILLARROEL M, CAMÙ E, ESCALONA N, ÁVILA P, RASMUSSEN S B, BAEZA P, GIL-LLAMBIAS F. Synergisms via hydrogen spillover between some transition metals during hydrodesulphurization: Increased activity towards conversion of refractory molecules[J]. Appl Catal A: Gen, 2011, 399(1/2): 63-68.

VALDEVENITO F, GARC A R, ESCALONA N, GIL-LLAMBIAS F J, RASMUSSEN S B, LÓPEZ-AGUDO A. Ni//Mo synergism via hydrogen spillover, in pyridine hydrodenitrogenation[J]. Catal Commun, 2010, 11(14): 1154-1156.

LIU L, LIU B, CHAI Y, LIU Y, LIU C. Synergetic effect between sulfurized Mo/γ-Al₂O₃ and Ni/γ-Al₂O₃ catalysts in hydrodenitrogenation of quinoline[J]. J Nat Gas Chem, 2011, 20(2): 214-217.

RODRIGUEZ J A, KIM J Y, HANSON J C, SAWHILL S J, BUSSELL M E. Physical and chemical properties of MoP, Ni₂P, and MoNiP hydrodesulfurization catalysts: Time-resolved X-ray diffraction, density functional, and hydrodesulfurization activity studies[J]. J Phys Chem B, 2003, 107(26): 6276-6285.

KIM J H, MA X, SONG C, LEE Y K, OYAMA S T. Kinetics of two pathways for 4,6-dimethyldibenzothiophene hydrodesulfurization over NiMo, CoMo sulfide, and nickel phosphide catalysts[J]. Energy Fuels, 2005, 19(2): 353-364.

LU M, WANG A, LI X, DUAN X, TENG Y, WANG Y, SONG C, HU Y. Hydrodenitrogenation of quinoline catalyzed by MCM-41-supported nickel phosphides[J]. Energy Fuels, 2007, 21(2): 554-560.

YANG S, LIANG C, PRINS R. A novel approach to synthesizing highly active Ni₂P/SiO₂ hydrotreating catalysts[J]. J Catal, 2006, 237(1): 118-130.

GUAN Q, LI W. The synthesis and evaluation of highly active Ni₂P-MoS₂ catalysts using the decomposition of hypophosphites[J]. Catal Sci Technol, 2012, 2(11): 2356-2360.

LIU L, LI G, LIU B, LIU D, LIU Y, LIU C. Hydrodesulfurization performence study of Ni₂P-modiffied MoS₂/Al₂O₃ catalysts[J]. Chem Ind Eng Soc Chin, 2011, 62(5): 1296-1231.

MCDONALD J W, FRIESEN G D, ROSENHEIN L D, NEWTON W E. Syntheses and characterization of ammonium and tetraalkylammonium thiomolybdates and thiotungstates[J]. Inorg Chim Acta, 1983, 72: 205-210.

PRINS R. Hydrogen spillover. Facts and fiction[J]. Chem Rev, 2012, 112(5): 2714-2738.

KHOOBIAR S. Particle to particle migration of hydrogen atoms on platinum-alumina catalysts from particle to neighboring particles[J]. J Phys Chem, 1964, 68(2): 411-412.

ARAI M, FUKUSHIMA M, NISHIYAMA Y. Interrupted-temperature programmed desorption of hydrogen over silica-supported platinum catalysts: The distribution of activation energy of desorption and the phenomena of spillover and reverse spillover of hydrogen[J]. Appl Surf Sci, 1996, 99(2): 145-150.

LIU X, CHEN J, ZHANG J. Hydrodechlorination of chlorobenzene over silica-supported nickel phosphide catalysts[J]. Ind Eng Chem Res, 2008, 47(15): 5362-5368.

SHI G, SHEN J. New synthesis method for nickel phosphide nanoparticles: Solid phase reaction of nickel cations with hypophosphites[J]. J Mater Chem, 2009, 19: 2295-2297.

OYAMA S T, WANG X, LEE Y K, CHUN W J. Active phase of Ni₂P/SiO₂ in hydroprocessing reactions[J]. J Catal, 2004, 221(2): 263-273.

VILLARROEL M, BAEZA P, GRACIA F, ESCALONA N, AVILA P, GIL-LLAMBIAS F J. Phosphorus effect on Co//Mo and Ni//Mo synergism in hydrodesulphurization catalysts[J]. Appl Catal A: Gen, 2009, 364(1/2): 75-79.

FAN Y, XIAO H, SHI G, LIU H, QIAN Y, WANG T, GONG G, BAO X. Citric acid-assisted hydrothermal method for preparing NiW/USY-Al₂O₃ ultradeep hydrodesulfurization catalysts[J]. J Catal, 2011, 279(1): 27-35.

Relative Articles

Supplements(0)

Cited By

Proportional views