Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

OP-V-3CATALYTIC HYDRODEOXYGENATION OF ANISOLE AS A MODELCOMPOUND OF BIO-OILS.A. Khromova, O.A. Bulavchenko, D.Yu. Ermakov, M.Yu. Lebedev,V.A. Yakovlev, V.N. ParmonBoreskov Institute of Catalysis, Pr. Akad. Lavrentieva, 5, Novosibirsk 630090, RussiaE-mail: khromova@catalysis.ruCrude bio–oil produced from biomass pyrolysis is the multi-component mixturecomposed of the various compounds derived from cellulose, hemicellulose and lignindepolymerization and fragmentation. All these aromatic and aliphatic alcohols, ethers,ketones, carboxylic acids and water cause the high oxygen content in bio-oil. The differencebetween the fossil hydrocarbon fuels and bio-oil is due to such properties of pyrolysis liquidas high viscosity, non-volatility, poor calorific value, corrosiveness, immiscibility with fossilfuels, thermal instability and trend to polymerization on storage and transportation. Thereforebio-oil upgrading is required to reduce oxygen content. Conventional oil – refininghydrocracking catalysts are commonly used for bio-oil deoxygenation. Typical catalysts forthis process are Co - Mo and Ni - Mo supported on alumina used in the sulfided form. Themain problems of these catalysts are rapid deactivation caused by sulfur loss and cokeformation. The use of non-sulfided catalysts for hydrodeoxygenation (HDO) process has beenconsidered to a far lesser extent. The aim of the present work was to develop and to test a non– sulfided and free of noble metals HDO catalyst. At first a number of catalysts based on thevarious active metals and using various supports were prepared and tested in HDO of modelbio-oil compound. In addition the same tests were run with the commercial oil processingsulfided catalysts. The results of the screening showed that the highest yields of hydrogenatedproducts are achieved over the Ni-Cu – based catalysts. Therefore this catalytic system waschosen for the further inquiry. The effect of copper loaded into the Ni-Cu catalysts onselectivity of the HDO reaction was determined by using TPR and XDR techniques as well asthe catalytic tests.Hydrodeoxygenation of anisole was carried out in a flow fixed bed reactor at 300 o C and1.0 MPa. Anisole was chosen as a model compound for methoxy functional groups of ligninin pyrolisys oil. HDO reaction over the Ni-Cu catalysts gives both aromatic and aliphatichydrocarbons, the main reaction products were benzene and cyclohexane, their oxygenatedderivatives - phenol, methyl substituted phenols, cyclohexanole and cyclohexanone wereobtained in smaller amounts. Products formed via methyl transfer to benzene ring (tolueneand methylcyclohexane) were also detected as the reaction products. All the Ni-Cu – based171