Catalytic Deoxygenation of Bio-Oil Model Compounds over Acid-Base Bifunctional Catalysts

被引:35
|
作者
Zhang, Jing [1 ]
Wang, Kaige [2 ]
Nolte, Michael W. [1 ]
Choi, Yong S. [1 ]
Brown, Robert C. [2 ]
Shanks, Brent H. [1 ]
机构
[1] Iowa State Univ, Dept Chem & Biol Engn, Ames, IA 50011 USA
[2] Iowa State Univ, Bioecon Inst, Ames, IA 50011 USA
来源
ACS CATALYSIS | 2016年 / 6卷 / 04期
关键词
acid-base bifunctional catalyst; bio-oil model compounds; catalytic pyrolysis; deoxygenation; mixed-metal oxides; AMORPHOUS SILICA-ALUMINA; H-1 MAS NMR; FAST PYROLYSIS; MINERAL CARBONATION; HYDROXYAPATITE CATALYSTS; FRAGMENTATION MECHANISMS; RESONANCE SPECTROSCOPY; CARBOHYDRATE PYROLYSIS; ALDOL CONDENSATIONS; AROMATIC PRODUCTION;
D O I
10.1021/acscatal.6b00245
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An acid-base bifunctional catalyst was synthesized by treating a natural mixed-metal oxide, serpentine, with sulfuric acid. Catalyst characterization revealed that the number of acidic and basic sites increased after the acid treatment largely due to an increase in surface area. However, stronger acid sites were also introduced by the formation of bridged hydroxyl groups between a Si atom and a heteroatom, as inferred by H NMR and NH3-TPD analysis. Results from SEM-EDS and H-1 NMR suggested that the acid and base sites were in close proximity. Catalytic conversions of carbohydrate-derived bio-oil model compounds were performed over different acid/base catalysts. Eight single bio-oil model compounds and two binary found to be strongly correlated to the number of oxygen containing functional groups in the reactant. The results from the binary mixtures showed that the acid base bifunctional catalyst had the highest activity in aldol condensation reactions. The best deoxygenation performance was also observed with the bifunctional catalyst for the model compounds. Reaction pathways were proposed on the basis of an isotope labeling study. Deoxygenation reactions were found to be promoted by the cooperative catalysis between closely located acid and base sites.mixtures were used. The reactivity of the model compounds was found to be strongly correlated to the number of oxygen containing functional groups in the reactant. The results from the binary mixtures showed that the acid base bifunctional catalyst had the highest activity in aldol condensation reactions. The best deoxygenation performance was also observed with the bifunctional catalyst for the model compounds. Reaction pathways were proposed on the basis of an isotope labeling study. Deoxygenation reactions were found to be promoted by the cooperative catalysis between closely located acid and base sites.
引用
收藏
页码:2608 / 2621
页数:14
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