Development Of New Catalytic Systems For Upgraded Bio-Fuels Production From Bio-Crude-Oil And Biodiesel

Catalysis Today 144 (2009) 362–366

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Development of new catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel
V.A. Yakovlev a,*, S.A. Khromova a, O.V. Sherstyuk a, V.O. Dundich a,b, D.Yu. Ermakov a, V.M. Novopashina a, M.Yu. Lebedev a, O. Bulavchenkoa, V.N. Parmon a,b
a b

Boreskov Institute of Catalysis, Pr. Akad. Lavrentieva 5, SB RAS, Novosibirsk 630090, Russia Novosibirsk State University, ul. Pirogova 2, Novosibirsk 630090, Russia

A R T I C L E I N F O

A B S T R A C T

Article history: Available online 7 April 2009 Keywords: Biomass Catalyst Hydrodeoxygenation Hydrotreatment Bio-oil Bioliquid

The investigation of upgradedbio-fuels production processes was carried out via the development of efficient catalysts for oxy-organic hydrodeoxygenation (HDO) processes. It was found that Ni–Cu catalysts are more attractive than single Ni catalysts in HDO under mild conditions. Copper facilitates the nickel oxide reduction at temperatures lower than 300 8C. Moreover, copper prevents methanization of oxy-organics at 280–3508C. The catalyst supports play also a key role in hydrotreatment of oxygencontaining compounds. Screening of catalyst supports showed that CeO2 and ZrO2 are most effective in the target processes because of possible additional activation of oxy-compounds on the support surface. The prepared catalysts have non-sulfided nature and can be used for upgrading of bioliquids with a low sulfur content. ß2009 Elsevier B.V. All rights reserved.

1. Introduction The petroleum consumption has surged during the 20th century, at least partially because of the rise of the automobile industry. Today, fossil fuels such as coal, oil and natural gas provide more than three quarters of the world’s energy consumption. On the other hand, biomass of plants can serve as a source for both energy and motorfuels, and being renewable it is the only sustainable source of energy and hydrocarbons for industry and automobile society. At present, biodiesel and bioethanol can be a substitute for the conventional fuels. The other promising feedstock for the engine fuels’ production is bio-oil—the liquid product of biomass flash pyrolysis [1]. However, this crude bio-oil cannot be used directly as a fuel forspark engines because of its poor operational characteristics. The main reason of low quality of biocrude-oil is the high content of oxygen. And whereas biodiesel and bioethanol can serve as improving additives to the conventional hydrocarbon fuel, in the case of pyrolysis oil, its catalytic pretreatment is required for the removal of oxygen and increasing the content of hydrogen in the liquid.Recently, a number of publications appeared in the field of hydrodeoxygenation (HDO) of the esters of fatty acids (biodiesel) [2–5]. These studies were initiated by the need for upgrading

* Corresponding author. E-mail address: yakovlev@catalysis.ru (V.A. Yakovlev). 0920-5861/$ – see front matter ß 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.cattod.2009.03.002

biodiesel and bio-oil asfuels for spark engines. The majority of researchers use conventional hydrodesulfurization (HDS) catalysts—sulfided Co–Mo and Ni–Mo supported on alumina—for the HDO reaction. However, the employment of HDS catalysts requires the addition of sulfur-containing compounds, for example H2S or thiophene, in the reaction zone for keeping the catalysts in the active form. Numerous studies on catalytic HDOof bio-crude-oil were reviewed in detail by Bridgwater et al. [6] and Elliott [7]. The HDO of pyrolysis liquid is commonly carried out in the presence of sulfided Co–Mo and Ni–Mo catalysts, as in the case of biodiesel. It should be noted that conventional HDS catalysts for oil refinery are not suitable for the bio-crude-oil or biodiesel hydrotreating because of a low sulfur content in the initial...