CoMo/Ti-SBA-15 catalysts for dibenzothiophene desulfurization

被引:102
作者
Nava, R.
Ortega, R. A.
Alonso, G.
Ornelas, C.
Pawelec, B.
Fierro, J. L. G.
机构
[1] Univ Nacl Autonoma Mexico, CFATA, Queretaro 76000, Mexico
[2] Univ Nacl Autonoma Mexico, Fac Quim, Mexico City 76010, DF, Mexico
[3] SC Complejo Ind Chihuahua, CIMAV, Chihuahua 3109, Mexico
[4] CSIC, Inst Catalisis & Petroleoquim, E-28049 Madrid, Spain
关键词
CoMo; Ti-SBA-15; MCM-41; SBA-15; dibenzothiophene; hydrodesulfurization;
D O I
10.1016/j.cattod.2007.02.034
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
With a view to reducing the sulfur content in diesel fuels, novel desulfurization CoMo catalysts were supported on a Ti-loaded hexagonal mesoporous SBA-15 material. The Ti-SBA-15 substrates were synthesized using triblock copolymers as structure-directing agents. Catalytic activity was assessed in the model reaction of hydrodesuffurization (HDS) of dibenzothiophene (DBT), carried out in a batch reactor at T = 623 K and with a total hydrogen pressure of 3.1 MPa. The reaction proceeds via the direct desulfurization route (main route) and the hydrogenation (HYD) pathway. The incorporation of Ti into the SBA-15 afforded catalysts that were more active than the Ti-free counterpart, due to the enhancement of the DDS route in this reaction. This difference was explained in terms of a larger number of coordinately unsaturated sites (CUS) of the metal sulfide on Ti-loaded catalysts. Under steady-state conditions, the CoMoST20 catalyst with a Si/Ti ratio of 20 was the most active among the catalysts studied. Since this catalyst exhibited both Ti4+ ions incorporated into the SBA-15 framework and separate anatase TiO2 clusters located on its surface, the activity enhancement on this sample was explained by the larger intrinsic activity of the "Co-Mo-S" phase located on these TiO2 nanoparticles. The Ti-SBA-15 supports and the CoMo/Ti-SBA-15 catalysts were studied by N-2 adsorption-desorption isotherms, XRD, TEM, FTIR of adsorbed pyridine and NO, UV-vis DRS, TPR, micro-Raman and XPS spectroscopy. (C) 2007 Elsevier B.V. All rights reserved.
引用
收藏
页码:70 / 84
页数:15
相关论文
共 75 条
[61]   Evaluation of metal oxide phase assembling mode inside the nanotubular pores of mesostructured silica [J].
Vradman, L ;
Landau, MV ;
Kantorovich, D ;
Koltypin, Y ;
Gedanken, A .
MICROPOROUS AND MESOPOROUS MATERIALS, 2005, 79 (1-3) :307-318
[62]   High loading of short WS2 slabs inside SBA-15:: promotion with nickel and performance in hydrodesulfurization and hydrogenation [J].
Vradman, L ;
Landau, MV ;
Herskowitz, M ;
Ezersky, V ;
Talianker, M ;
Nikitenko, S ;
Koltypin, Y ;
Gedanken, A .
JOURNAL OF CATALYSIS, 2003, 213 (02) :163-175
[63]  
Wagner C. D., 1979, HDB XRAY PHOTOELECTR
[64]   Hydrodesulfurization of dibenzothiophene over siliceous MCM-41-supported catalysts - II. Sulfided Ni-Mo catalysts [J].
Wang, AJ ;
Wang, Y ;
Kabe, T ;
Chen, YY ;
Ishihara, A ;
Qian, WH ;
Yao, PJ .
JOURNAL OF CATALYSIS, 2002, 210 (02) :319-327
[65]   Hydrodesulfurization of dibenzothiophene over siliceous MCM-41-supported catalysts I. Sulfided Co-Mo catalysts [J].
Wang, AJ ;
Wang, Y ;
Kabe, T ;
Chen, YY ;
Ishihara, A ;
Qian, WH .
JOURNAL OF CATALYSIS, 2001, 199 (01) :19-29
[66]   Synthesis of SBA-15 with different pore sizes and the utilization as supports of high loading of cobalt catalysts [J].
Wang, Y ;
Noguchi, M ;
Takahashi, Y ;
Ohtsuka, Y .
CATALYSIS TODAY, 2001, 68 (1-3) :3-9
[67]   Hydrodesulfurization of dibenzothiophenes over molybdenum catalyst supported on TiO2-Al2O3 [J].
Yoshinaka, S ;
Segawa, K .
CATALYSIS TODAY, 1998, 45 (1-4) :293-298
[68]   Removal of refractory S-containing compounds from liquid fuels on novel bifunctional CoMo/HMS catalysts modified with Ti [J].
Zepeda, T. A. ;
Pawelec, B. ;
Fierro, J. L. G. ;
Halachev, T. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2007, 71 (3-4) :223-236
[69]   Effect of Ti on the catalytic properties of CoMo/Ti(x)-HMS catalysts in the reaction of hydrodesulfurization of 4-ethyl-6-methyl dibenzothiophene [J].
Zepeda, T. A. ;
Pawelec, B. ;
Fierro, J. L. G. ;
Halachev, T. .
JOURNAL OF CATALYSIS, 2006, 242 (02) :254-269
[70]   Hydrodesulfurization of dibenzothiophene over CoMo/HMS and CoMo/Ti-HMS catalysts [J].
Zepeda, TA ;
Halachev, T ;
Pawelec, B ;
Nava, R ;
Klimova, T ;
Fuentes, GA ;
Fierro, JLG .
CATALYSIS COMMUNICATIONS, 2006, 7 (01) :33-41