水热法合成Ni-Mo非负载型催化剂及催化加氢性能

石油炼制与化工 ›› 2013, Vol. 44 ›› Issue (9): 19-24.

水热法合成Ni-Mo非负载型催化剂及催化加氢性能

刘欢,殷长龙,赵蕾艳,刘晨光

中国石油大学（华东）重质油国家重点实验室 CNPC催化重点实验室

收稿日期:2013-01-21 修回日期:2013-03-08 出版日期:2013-09-12 发布日期:2013-08-27
通讯作者: 殷长龙 E-mail:yincl@upc.edu.cn
基金资助:
国家重点基础研究发展计划“973”项目;教育部自主创新科研计划新项目资助;中国石油大学（华东）研究生创新工程项目资助

HYDROTHERMAL SYNTHESIS OF Ni-Mo UNSUPPORTED CATALYST AND THEIR CATALYTIC PERFORMANCE

Received:2013-01-21 Revised:2013-03-08 Online:2013-09-12 Published:2013-08-27

摘要/Abstract

摘要： 采用水热反应法合成了一系列NiMo不同比例的多孔复合金属氧化物，用XRD、BET、SEM表征手段对其结构、孔性质等进行了表征，并将NiMo复合金属氧化物制备成非负载型NiMo加氢催化剂，在连续流动高压微反装置上考察了其加氢脱硫、加氢脱氮和芳烃加氢饱和反应活性。结果表明，这几种复合金属氧化物是具有钼酸镍铵晶相的物质，并且随着镍含量的增加，合成的NiMo复合金属氧化物的比表面积和孔容呈现线性增加的趋势，而孔径则表现出双介孔的特征。催化评价结果表明，当NiMo比例为1:1时，制备的非负载型催化剂具有最高的催化加氢性能，并采用“火山模型”对活性差异进行了讨论。

Abstract: The composite metal oxides with different Ni-Mo atomic ratio were synthetized by hydrothermal reaction and characterized by XRD、BET and SEM. The unsupported catalysts were prepared from the composite metal oxides and their activities of HDS, HDN and HYD were evaluated in a continuous flow high-pressure micro reactor. The results show that the composite metal oxides are mainly composed of ammonium nickel molybdate, while the phase of Ni3S2 and MoS2 are detected in the unsupported sulfided catalysts. N2 adsorption-desorption characterization indicate that the composite oxides exhibits the bimodal mesoporous structures, and the specific surface area and pore volume increase with increasing amount of basic nickel carbonate tetrahydrate. Catalytic results manifest that the unsupported Ni-Mo catalyst with the Ni-Mo ratio of 1:1 has better hydrogenation activity: HDS of DBT is 100%, while HDN of quinoline and HYD of naphthalene reach 62.3% and 27.3%, respectively.

刘欢殷长龙赵蕾艳刘晨光. 水热法合成Ni-Mo非负载型催化剂及催化加氢性能[J]. 石油炼制与化工, 2013, 44(9): 19-24.

参考文献

[1] Fujikawa T, Kimura H, Kiriyama K, et al. Development of ultra-deep HDS catalyst for production of clean diesel fuels[J]. Catalysis Today, 2006, 111(3-4): 188-193
[2] Breysse M, Afanasiev P, Geantet C, et al. Overview of support effects in hydrotreating catalysts[J]. Catalysis Today, 2003, 86(1-4): 5-16
[3] Al-Daous A, Ali A. Deep desulfurization of gas oil over NiMo catalysts supported on alumina–zirconia composites[J]. Fuel, 2012, 97: 662-669
[4] Eijsbouts S, Mayo W, Fujita K. Unsupported transition metal sulfide catalysts: From fundamentals to industrial application[J]. Applied Catalysis A: General, 2007, 322: 58-66
[5] Alvarez L, Espino J, Ornelas C, et al. Comparative study of MoS2 and Co/MoS2 catalysts prepared by ex situ/in situ activation of ammonium and tetraalkylammonium thiomolybdates[J]. Journal of Molecular Catalysis A: Chemical, 2004, 210(1-2): 105-117
[6] Centi G, Perathoner S. Catalysis by layered materials: A review[J]. Microporous and Mesoporous Materials, 2008, 107(1-2): 3-15
[7] Sun M, Nicosia D, Prins R. The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis[J]. Catalysis Today, 2003, 86(1-4): 173-189
[8] Chianelli R, Berhault G, Torres B. Unsupported transition metal sulfide catalysts: 100 years of science and application[J]. Catalysis Today, 2009, 147(3-4): 275-286
[9] Yoosuk B, Kim H, Song C, et al. Highly active MoS2, CoMoS2 and NiMoS2 unsupported catalysts prepared by hydrothermal synthesis for hydrodesulfurization of 4,6-dimethyldibenzothiophene[J]. Catalysis Today, 2008, 130(1): 14-23
[10] Nava H, Ornelas C, Aguilar A, et al. Cobalt-Molybdenum Sulfide Catalysts Prepared by In Situ Activation of Bimetallic (Co-Mo) Alkylthiomolybdates[J]. Catalysis Letters, 2003, 86: 257-265
[11] Nava H, Pedraza F, and Alonso G. Nickel-Molybdenum-Tungsten Sulfide catalysts prepared by in situ activation of tri-metallic (Ni-Mo-W) alkylthiomolybdotungstates[J]. Catalysis Letters, 2005, 99: 65-71
[12] Yi Y, Zhang B, Jin X, et al. Unsupported NiMoW sulfide catalysts for hydrodesulfurization of dibenzothiophene by thermal decomposition of thiosalts[J]. Journal of Molecular Catalysis A: Chemical, 2011, 351: 120-127
[13] Huirache-Acu?a R, Albiter A, Espino J, et al. Synthesis of Ni–Mo–W sulphide catalysts by ex situ decomposition of trimetallic precursors[J]. Applied Catalysis A: General, 2006, 304: 124-130
[14] Olivas A, Galván H, Alonso G, et al. Trimetallic NiMoW unsupported catalysts for HDS[J]. Applied Catalysis A: General, 2009, 352(1-2): 10-16
[15] Kunisada N, Choi K, Korai Y, et al. Novel zeolite based support for NiMo sulfide in deep HDS of gas oil[J]. Applied Catalysis A: General, 2004, 269(1-2): 43-51
[16] Klimova T, Reyes J, Gutiérrez O, et al. Novel bifunctional NiMo/Al-SBA-15 catalysts for deep hydrodesulfurization: Effect of support Si/Al ratio[J]. Applied Catalysis A: General, 2008, 335(2): 159-171
[17] Saih Y, Nagata M, Funamoto T, et al. Ultra deep hydrodesulfurization of dibenzothiophene derivatives over NiMo/TiO2-Al2O3 catalysts[J]. Applied Catalysis A: General, 2005, 295(1): 11-22
[18] Levin D, Soled S, Ying J. Crystal Structure of an Ammonium Nickel Molybdate Prepared by Chemical Precipitation[J]. Ingorganic Chemistry, 1996, 35: 4191-4197
[19] Zhou T, Yin H, Liu Y, et al. Synthesis, Characterization and HDS Activity of Carbon-Containing Ni–Mo Sulfide Nano-Spheres[J]. Catalysis Letters, 2009, 134(3-4): 343-350
[20] Ho T. Deep HDS of diesel fuel: chemistry and catalysis[J]. Catalysis Today, 2004, 98(1-2): 3-18
[21] Pecoraro T, Chianelli R. Hydrodesulfurization catalysis by transition metal sulfides[J]. Journal of Catalysis, 1981, 67: 430-445
[22] Toulhoat H. Kinetic interpretation of catalytic activity patterns based on theoretical chemical descriptors[J]. Journal of Catalysis, 2003, 216(1-2): 63-72
[23] Dinter N, Rusanen M, Raybaud P, et al. Temperature-programed reduction of unpromoted MoS2-based hydrodesulfurization catalysts: Experiments and kinetic modeling from first principles[J]. Journal of Catalysis, 2009, 267(1): 67-77
[24] Toulhoat H, Raybaud P, Kasztelan S, et al. Transition metals to sulfur binding energies relationship to catalytic activities in HDS: back to Sabatier with first principle calculations[J]. Catalysis Today, 1999, 50: 629-636
[25] Daudin A, Brunet S, Perot G, et al. Transformation of a model FCC gasoline olefin over transition monometallic sulfide catalysts[J]. Journal of Catalysis, 2007, 248(1): 111-119
[26] Daudin A, Lamic F, Pérot G, et al. Microkinetic interpretation of HDS/HYDO selectivity of the transformation of a model FCC gasoline over transition metal sulfides[J]. Catalysis Today, 2008, 130(1): 221-230