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One step hydrogenation-esterification of model compounds and bio-oil to alcohols and esters over Raney Ni catalysts

Authors
  • ying, xu
  • limin, zhang
  • jiamin, chang
  • xinghua, zhang
  • longlong, ma
  • tiejun, wang
  • zhang, qi
Publication Date
Jan 15, 2016
Source
GuangZhou Institute of Energy Conversion
Keywords
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Unknown
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Abstract

Acids, aldehydes, ketones and phenols, which are the main components of bio-oil, have negative effects on the properties. In this paper, the mixture of acetic acid, furfural, hydroxyacetone, ethanediol, phenol and water were chosen as hybrid model compounds of bio-oil (MCB). To convert these compounds into stable and combustible oxygenated organics (alcohols and esters), one step hydrogenation-esterification (OHE) was carried out over Raney Ni catalyst (RN) and Mo, Sn, Fe, Cu modified Raney Ni catalysts (RNs) in the presence of methanol. 100% conversions of furfural and hydroxyacetone were achieved over RNs with high selectivity to desired products. The acetic acid conversion was only 35.1% with no methanol addition, while within 6 g/8 g methanol/MCB addition, the conversion of acetic acid increased to 81.1%. The esterification activity of alcohols was followed by methanol > tetrahydrofurfuryl alcohol (THFA), the hydrogenation product of furfural > ethanediol. Among the RNs, the addition of Fe catalyst restrained the aqueous-phase reforming of methanol and promoted the esterification of methanol and acetic acid. The Mo-RN showed the most favorable performance in the hydrogenation of phenol among the RNs. But the RN modified by both Fe and Mo did not give a good performance. After the OHE of light fraction of raw bio-oil over Mo-RN, there was no ketone & aldehyde detected and the contents of acids and phenols decreased from 49.04% and 7.35% to 8.21% and 3.84%. The conversion of acids could reach to 85.01% which was nearly to the conversion of acetic acid in MCB. The contents of alcohols and esters increased from 5.79% and 4.74% to 53.61% and 33.66%. The content of stable and combustible oxygenated organics reached to 87.27% after OHE of light fraction of raw bio-oil. (C) 2015 Elsevier Ltd. All rights reserved.

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