Study of the Hydrodeoxygenation of Carbonyl, Carboxylic and Guaiacyl Groups Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalysts .1. Catalytic Reaction Schemes

The elimination of specific oxygenated groups of biomass-derived pyrolysis oils (bio-oils) is necessary for improving their stability. These are mainly unsaturated groups like alkene, carbonyl and carboxylic functions, as well as guaiacyl groups. For practical applications, it is desirable that the reactions are performed selectively in order to avoid excessive hydrogen consumption. The reactions must be done at relatively low temperature in order to limit competitive thermal condensation reactions. In this study, model oxygenated compounds were used, namely 4-methylacetophenone, diethyldecanedioate and guaiacol. They were tested simultaneously in one reaction test in the presence of sulfided cobalt-molybdenum and nickel-molybdenum supported on gamma-alumina catalysts in a batch system. Their reactivity and conversion scheme were determined. The ketonic group is easily and selectively hydrogenated into a methylene group at temperatures higher than 200 degrees C. Carboxylic groups are also hydrogenated to methyl groups, but a parallel decarboxylation occurs at comparable rates. A temperature around 300 degrees C is required for the conversion of carboxylic groups as well as for the conversion of the guaiacyl groups. The main reaction scheme of guaiacol is its transformation in hydroxyphenol which is subsequently converted to phenol. But in batch reactor conditions, guaiacol gives a high proportion of heavy products. CoMo and NiMo catalysts have comparable activities and selectivities. However, the NiMo catalyst has a higher decarboxylating activity than CoMo and also leads to a higher proportion of heavy products during the conversion of guaiacol.

[1]  M. Ledoux,et al.  Comparative hydrodenitrogenation activity of molybdenum, Co–Mo and Ni–Mo alumina-supported catalysts , 1990 .

[2]  Michael T. Klein,et al.  Influence of water on guaiacol pyrolysis , 1985 .

[3]  F. P. Petrocelli,et al.  MODELING LIGNIN LIQUEFACTION 1. CATALYTIC HYDROPROCESSING OF LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES , 1987 .

[4]  B. Delmon,et al.  Influence of oxygen-, nitrogen-, and sulfur-containing compounds on the hydrodeoxygenation of phenols over sulfided cobalt-molybdenum/.gamma.-alumina and nickel-molybdenum/.gamma.-alumina catalysts , 1993 .

[5]  C. Satterfield,et al.  Poisoning of thiophene hydrodesulfurization by nitrogen compounds , 1988 .

[6]  A. Sapre,et al.  Hydrogenation of aromatic compounds catalyzed by sulfided CoOMoO3γ-Al2O3 , 1982 .

[7]  C. Satterfield,et al.  Some effects of sulfiding of a NiMoAl2O3 catalyst on its activity for hydrodenitrogenation of quinoline , 1983 .

[8]  G. Schuit,et al.  The CoO---MoO3---Al2O3 catalyst : III. Catalytic properties , 1969 .

[9]  M. Huuska,et al.  Hydrogenolysis of differently substituted methoxyphenols , 1989 .

[10]  P. Geneste,et al.  Catalytic hydrogenation of cycloalkanones on PtSiO2 and RuSiO2: The effects of ring size , 1979 .

[11]  G. Pérot The reactions involved in hydrodenitrogenation , 1991 .

[12]  P. Schleyer,et al.  Heterogeneous deoxygenation of ketones , 1981 .

[13]  C. Moreau,et al.  Heterogeneous hydrodeoxygenation of ketones and alcohols on sulfided NiOMoO3γ−Al2O3 catalyst , 1984 .

[14]  D. Ollis,et al.  Catalytic hydrodeoxygenation: I. Conversions of o-, p-, and m-cresols , 1983 .

[15]  J. Lemberton,et al.  Catalytic hydroprocessing of simulated coal tars: I. Activity of a Sulphided Ni-Mo/Al2O3 Catalyst for the Hydroconversion of Model Compounds , 1989 .

[16]  R. Voorhoeve,et al.  Kinetics of hydrogenation on supported and bulk nickel-tungsten sulfide catalysts , 1971 .

[17]  B. Delmon,et al.  Influence of Oxygen-containing, Nitrogen-containing, and Sulfur-containing-compounds On the Hydrodeoxygenation of Phenols Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalysts , 1993 .

[18]  S. Kaliaguine,et al.  Catalytic hydrotreatment of vacuum pyrolysis oils from wood , 1988 .

[19]  G. Froment,et al.  Kinetics of hydrodesulfurization on a cobalt-molybdenum/.gamma.-alumina catalyst. 1. Kinetics of the hydrogenolysis of thiophene , 1986 .

[20]  J. Rintala,et al.  Effect of catalyst acidity on the hydrogenolysis of anisole , 1985 .

[21]  D. Boocock,et al.  Hydrodeoxygenation of hydroxy, methoxy and methyl phenols with molybdenum oxide/nickel oxide/alumina catalyst , 1985 .

[22]  J.B-son Bredenberg,et al.  Hydrogenolysis and hydrocracking of the carbon-oxygen bond. 2. Thermal cleavage of the carbon-oxygen bond in guaiacol , 1982 .

[23]  H. Mcilvried Kinetics of the Hydrodenitrification of Pyridine , 1971 .

[24]  Gérald Djéga-Mariadassou,et al.  Utilization of vegetable oils as an alternative source for diesel-type fuel: hydrocracking on reduced Ni/SiO2 and sulphided Ni-Mo/γ-Al2O3 , 1989 .

[25]  Paul von Ragué Schleyer,et al.  Hydrogenolysis, IV. Gas phase decarboxylation of carboxylic acids , 1982 .

[26]  M. Klein,et al.  Reaction pathway analysis of thermal and catalytic lignin fragmentation by use of model compounds , 1983 .

[27]  A. Vuori,et al.  Hydrogenolysis and Hydrocracking of the Carbon-Oxygen Bond. 4. Thermal and Catalytic Hydrogenolysis of 4-Propylguaiacol , 1984 .

[28]  F. Massoth,et al.  The effect of H2S on the hydrogenation and cracking of hexene over a CoMo catalyst , 1981 .

[29]  E. Furimsky,et al.  Chemistry of Catalytic Hydrodeoxygenation , 1983 .

[30]  D. C. Elliott,et al.  Analysis and comparison of biomass pyrolysis/gasification condensates: Final report , 1986 .

[31]  D. Duprez,et al.  Role of the support in the skeletal isomerization of 3,3-dimethyl-1-butene on oxided and sulfided CoMo/Al2O3 catalysts , 1991 .

[32]  B. Gevert,et al.  Kinetics of the HDO of methyl-substituted phenols , 1987 .

[33]  M. Huuska,et al.  Hydrogenolysis and hydrocracking of the carbon-oxygen bond: I. Hydrocracking of some simple aromatic O-compounds , 1982 .

[34]  J.B-son Bredenberg,et al.  Hydrogenolysis and hydrocracking of the carbonoxygen bond. 3. Thermolysis in tetralin of substituted anisoles , 1983 .

[35]  C. Satterfield,et al.  Effect of water on the catalytic reaction network of quinoline hydrodenitrogenation , 1986 .

[36]  D. M. Nace,et al.  Coke Formation and Its Relationship to Cumene Cracking , 1955 .