Hydrodesulfurization of 4,6-DMDBT on multi-metallic bulk catalyst NiAlZnMoW: Effect of Zn

被引:19
作者
Chen, Yandie [1 ,2 ]
Wang, Lu [1 ]
Liu, Xinyi [1 ]
Liu, Tiefeng [1 ]
Huang, Baokun [1 ]
Li, Ping [1 ]
Jiang, Zongxuan [1 ]
Li, Can [1 ]
机构
[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
[2] Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China
关键词
Layered structure; 4,6-Dimethyldibenzothiophene; Hydrodesulfurization; Multi-metallic bulk catalyst; Promoter effect; SULFIDE HYDROTREATING CATALYSTS; ZNNIMO/GAMMA-ALUMINA CATALYSTS; DIESEL FUELS; DEEP DESULFURIZATION; SPILLOVER HYDROGEN; HDS CATALYSTS; MOS2; CATALYST; NI; DIBENZOTHIOPHENE; SULFUR;
D O I
10.1016/j.apcata.2015.01.039
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Multi-metallic bulk HDS catalysts NixZnyAlzMoW with different Zn/Al molar ratio were prepared using a NiZnAl-layered hydroxide precursor by co-precipitation method. XRD, HRTEM, and SEM results show that the catalysts possess layered structure, and the layered precursor NixZnyAlz-LDH is a mixture of ZnAl-LDH and NiAl-LDH. Ni(Zn)-promoted Mo(W) active species Ni(Zn)-Mo(W)-S are detected by Raman spectroscopy and HRTEM. Hydrodesulfurization (HDS) result of 4,6-dimethyldibenzothiophene (4,6-DMDBT) shows that catalysts NixZnyAlzMoW exhibit excellent HDS performance and the sulfur content in the model diesel could be reduced from 517 ppm to less than 10 ppm (under mild reaction conditions of 3.0 MPa of H-2 pressure, 300 degrees C, LHSV of 9 h(-1), and H-2/oil ratio of 800 Ncm(3)/cm(3)). Catalysts NixZnyAlzMoW show higher HDS activity than the commercial catalyst CoNiMoW/Al2O3 due to the high active metal content, the layered structure, and the positive promoter effect of Zn. Besides, Zn-doping also reduces the apparent activation energy of catalysts and results in larger pore volume and larger pore size for catalysts. Part of Zn (Ni) acts as a promoter but other part as a support. The promoter effect of Zn is partially responsible for the high HDS activity. It is found that the second promoter Zn decreases the interaction between alumina and active components Ni, Mo, W to form more Ni(Zn)-Mo(W)-S active species. (C) 2015 Elsevier B.V. All rights reserved.
引用
收藏
页码:319 / 327
页数:9
相关论文
共 45 条
[1]  
Allas M.O., 1990, P INDIAN ACAD SCI CH, V102, P117
[2]   A Study on the Morphology of Unsupported Ni-Mo-W Sulfide Hydrotreating Catalysts Through High-resolution Transmission Electron Microscopy [J].
An, G. ;
Liu, C. ;
Xiong, C. ;
Lu, C. .
PETROLEUM SCIENCE AND TECHNOLOGY, 2012, 30 (15) :1599-1608
[3]  
[Anonymous], P 8 INT C CAT
[4]   Dibenzothiophene hydrodesulfurization over cobalt phosphide catalysts prepared through a new synthetic approach: Effect of the support [J].
Cecilia, J. A. ;
Infantes-Molina, A. ;
Rodriguez-Castellon, E. ;
Jimenez-Lopez, A. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2009, 92 (1-2) :100-113
[5]   A new multi-metallic bulk catalyst with high hydrodesulfurization activity of 4,6-DMDBT prepared using layered hydroxide salts as structural templates [J].
Chen, Yandie ;
Wang, Lu ;
Zhang, Yuliang ;
Liu, Tiefeng ;
Liu, Xinyi ;
Jiang, Zongxuan ;
Li, Can .
APPLIED CATALYSIS A-GENERAL, 2014, 474 :69-77
[6]   Intra- and inter-layer structures of layered hydroxy double salts, Ni1-xZn2x(OH)2(CH3CO2)2x•nH2O [J].
Choy, JH ;
Kwon, YM ;
Han, KS ;
Song, SW ;
Chang, SH .
MATERIALS LETTERS, 1998, 34 (3-6) :356-363
[7]   On the flexibility of the active phase in hydrotreating catalysts [J].
Eijsbouts, S .
APPLIED CATALYSIS A-GENERAL, 1997, 158 (1-2) :53-92
[8]   Nanometric bimetallic sulfides prepared via thermal decomposition of Ni and Fe heteropolymolybdate emulsions [J].
Escalona, Emir E. ;
Pereira-Almao, Pedro R. ;
Castillo, Jimmy ;
Hung, Jeannette ;
Bolivar, Carmelo ;
Scott, Carlos E. .
CATALYSIS LETTERS, 2006, 112 (3-4) :227-230
[9]   Competitive hydrodesulfurization of dibenzothiophene and hydrodenitrogenation of quinoline over unsupported MoS2 catalyst [J].
Farag, Hamdy ;
Kishida, Masahiro ;
Al-Megren, Hamid .
APPLIED CATALYSIS A-GENERAL, 2014, 469 :173-182
[10]   LDH nanocomposites with different guest entities as precursors of supported Ni catalysts [J].
Gerardin, Corine ;
Kostadinova, Dessislava ;
Coq, Bernard ;
Tichit, Didier .
CHEMISTRY OF MATERIALS, 2008, 20 (06) :2086-2094