Influence of Si/Al Ratio on Catalytic Performance of (Co)Mo/Saponite Catalysts

The influence of the Si/Al ratio of the support of (Co)Mo/saponite catalysts on the performance in the hydrodesulfurisation of thiophene and hydrocracking of n-decane has been studied. The initial thiophene HDS activity of the sulfided Co catalysts increased with increasing support acidity, while with the CoMo catalysts the opposite effect was observed. The large drop in activity at lower Si/Al ratios is ascribed to the occurrence of two separate cobalt and molybdenum sulfide phases instead of the “Co‐Mo‐S” phase. In the hydrocracking of n-decane both the Co and the CoMo catalysts displayed an almost linear relationship between the first-order rate constant and the number of Bronsted acid sites. As with zeolite catalysts the Si/Al ratio was also found to affect the product selectivity. At low Si/Al ratios the relative amount of secondary cracking products increased due to a changing balance between the number of cracking and hydrogenation sites. Remarkably, it was found that in the presence of H2S between 423 and 573 K the n-decane conversion passes through a maximum. The observed relation between this “low-temperature” activity and the number of Bronsted acid sites seem to indicate the involvement of both H2S and the acid sites on the support. c ∞ 1999 Academic Press

[1]  V. Hopkins,et al.  Evaluation of Potential 700° F. Hydraulic Fluids in a Pump Loop , 1964 .

[2]  W. Garwood,et al.  Mechanism of Hydrocracking. Reactions of Paraffins and Olefins , 1964 .

[3]  C. Baes,et al.  The hydrolysis of cations , 1986 .

[4]  H. Olphen An Introduction to Clay Colloid Chemistry , 1977 .

[5]  V. Zon,et al.  An EXAFS study of the structure of the metal–support interface in highly dispersed Rh/Al2O3 catalysts , 1985 .

[6]  P. Jacobs,et al.  Attempts to rationalize the distribution of hydrocracked products. I qualitative description of the primary hydrocracking modes of long chain paraffins in open zeolites , 1986 .

[7]  R. Burch,et al.  Zr-Containing pillared interlayer clays: I. Preparation and structural characterisation , 1986 .

[8]  F. Figueras,et al.  Pillared Clays as Catalysts , 1988 .

[9]  M. Occelli,et al.  Hydrotreating catalysts containing pillared clays , 1988 .

[10]  He Ming-yuan,et al.  Acidic and hydrocarbon catalytic properties of pillared clay , 1988 .

[11]  R. Gorte,et al.  Amine adsorption in H-ZSM-5 , 1990 .

[12]  D. Koningsberger,et al.  Influence of preparation method on the metal cluster size of platinum/ZSM-5 catalysts as studied with EXAFS , 1990 .

[13]  D. Koningsberger,et al.  Structure of the Molybdenum Sulfide Phase in Carbon-Supported Molybdenum and Cobalt-Molybdenum Sulfide Catalysts as Studied by EXAFS. , 1990 .

[14]  R. Prins,et al.  EXAFS Determination of the Structure of Cobalt in Carbon-Supported Cobalt and Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts. , 1991 .

[15]  J. Mathews,et al.  Hydrocracking and isomerization of n-octane and 2,2,4-trimethylpentane over a platinum/alumina-pillared clay , 1991 .

[16]  W. Stork,et al.  Chapter 15 Hydrocarbon Processing with Zeolites , 1991 .

[17]  D. M. Chapman,et al.  Isopropylamine adsorption for the characterization of acid sites in silica-alumina catalysts , 1992 .

[18]  J. W. Ward Hydrocracking processes and catalysts , 1993 .

[19]  Van Santen,et al.  Catalytic activity of nickel sulfide catalysts supported on Al-pillared montmorillonite for thiophene hydrodesulfurization , 1993 .

[20]  A. Agudo,et al.  Catalytic activity of Co, Mo and CoMo supported on NaY zeolite: hydrodesulfurization of gas oil at high pressure , 1994 .

[21]  E. Min Development of Pillared Clays for Industrial Catalysis , 1994 .

[22]  H. Zandbergen,et al.  HDS activity and characterization of zeolite-supported nickel sulfide catalysts , 1994 .

[23]  M. Sugioka,et al.  Hydrocarbon conversions over sodium zeolites in the presence of hydrogen sulfide , 1994 .

[24]  Van Santen,et al.  Some Aspects of the Preparation and Catalytic Activity of Chromia Pillared Montmorillonite , 1994 .

[25]  Van Santen,et al.  Influence of zeolite acidity on thiophene hydrodesulfurization activity , 1994 .

[26]  P. Jacobs,et al.  Hydroisomerization-Hydrocracking of Decane over Al- and Ga-Pillared Clays , 1994 .

[27]  J. T. Kloprogge,et al.  Synthesis of Al-pillared beidellite and its catalytic activity in the hydroconversion ofn-heptane , 1994 .

[28]  Jeffrey T. Miller,et al.  Hydrogen as a Modifier of the Structure and Electronic Properties of Platinum in Acidic Zeolite LTL: A Combined Infrared and X-ray Absorption Spectroscopy Study , 1995 .

[29]  R. Mokaya,et al.  Pillared clays and pillared acid-activated clays: A comparative study of physical, acidic, and catalytic properties , 1995 .

[30]  D. Koningsberger,et al.  A new method for parameterization of phase shift and backscattering amplitude , 1995 .

[31]  R. A. Santen,et al.  Hydrocracking of n-Decane over Zeolite-Supported Metal Sulfide Catalysts. 2. Zeolite Y-Supported Ni and Ni-Mo Sulfides , 1995 .

[32]  G. Djéga-Mariadassou,et al.  The nature of NiMo phases encaged in HY zeolites , 1995 .

[33]  Van Santen,et al.  Synthesis, characterization and catalytic activity of chromia pillared clays , 1995 .

[34]  F. Marcos The Use of Clays for the Hydrotreatment of Heavy Crude Oils , 1995 .

[35]  J. Geus,et al.  Non-hydrothermal synthesis, characterisation and catalytic properties of saponite clays , 1995 .

[36]  F. Ribeiro,et al.  Hydroisomerization and hydrocracking of alkanes. 7. Influence of the balance between acid and hydrogenating functions on the transformation of n-decane on PtHY catalysts , 1996 .

[37]  J. Houžvička,et al.  Skeletal isomerisation of n-butene on phosphorus containing catalysts , 1996 .

[38]  D. C. Koningsberger,et al.  Novel Hydrotreating Catalysts Based on Synthetic Clay Minerals , 1997 .

[39]  J. Geus,et al.  The Sulfidation of γ-Alumina and Titania Supported (Cobalt)Molybdenum Oxide Catalysts Monitored by EXAFS , 1997 .

[40]  J. Geus,et al.  A Mo–K Edge XAFS Study of the Metal Sulfide-Support Interaction in (Co)Mo Supported Alumina and Titania Catalysts , 1997 .

[41]  B. Delmon,et al.  Discovery of a new role of spillover hydrogen emitted by sulfided catalysts: creation of acidic sites on amorphous silica-alumina , 1997 .

[42]  J. Houžvička,et al.  The role of the density of active sites in skeletal isomerisation of n-butene , 1997 .

[43]  Roel Prins,et al.  Why EXAFS Underestimated the Size of Small Supported MoS2 Particles , 1998 .

[44]  J. Geus,et al.  Acidic properties of synthetic saponites studied by pyridine IR and TPD[ndash ]TG of n-propylamine , 1998 .

[45]  J. Geus,et al.  Structure and Nature of the Active Sites in CoMo Hydrotreating Catalysts Conversion of Thiophene , 1998 .