载体对其负载的Cu-Co双金属催化剂上5-羟甲基糠醛氢解选择性生成2,5-二甲基呋喃的影响

doi:10.1016/S1872-2067(17)62789-X

摘要/Abstract

摘要：

碳-氧键氢解是生物质呋喃基化合物制备交通燃料常见的模型反应，其中5-羟甲基糠醛（HMF）转化为汽油添加剂2，5-二甲基呋喃（DMF）尤为引人关注.本文采用CeO₂，ZrO₂和Al₂O₃负载的Cu-Co双金属催化剂用于HMF选择性氢解制DMF的反应中.采用X射线衍射、N₂吸附-脱附、投射电镜、H₂-程序升温还原、氨-程序升温脱附和元素分析表征了新鲜的和使用过催化剂的结构，并将其与催化活性相关联.Cu-Co/CeO₂催化剂通过在大的Cu颗粒上还原C=O键生成了最多的2，5双（羟甲基呋喃）（BHMF）.但Cu-Co/Al₂O₃催化剂具有高度分散的Cu，Cu-Co复合氧化物和大量的弱酸位，因而生成DMF的选择性最高.Cu-Co/ZrO₂催化剂则由于存在强酸位，DMF选择性较低，生成了各种过度氢解产物，如2，5而甲基四氢呋喃和5，5-二（亚甲基）双（2-甲基呋喃）.因此，考察了Cu-Co/Al₂O₃催化剂上的反应路径，以及温度、氢气压力和时间等操作条件的影响，使其具有较优的HMF转化率和DMF选择性.

关键词: 羟甲基糠醛, 加氢, 氢解, 铜-钴, 双金属, 生物燃料

Abstract:

The hydrogenolysis of carbon-oxygen bonds is an important model reaction in upgrading biomass-derived furanic compounds to transportation fuels. One of these model reactions, namely conversion of 5-hydroxymethylfurfural (HMF) to the gasoline additive 2,5-dimethylfuran (DMF), is especially attractive. In this study, bimetallic Cu-Co catalysts supported on CeO₂, ZrO₂, and Al₂O₃were used for the selective hydrogenolysis of HMF to DMF. The structures of the fresh and used catalysts were studied using X-ray diffraction, the Brunauer-Emmett-Teller method, transmission electron microscopy, temperature-programmed reduction by H₂, temperature-programmed desorption of NH₃, and CHNS analysis. The structures were correlated with the catalytic activities. The Cu-Co/CeO₂ catalyst produced mainly 2,5-bis(hydroxymethyl)furan via reduction of C=O bonds on large Cu particles. The Cu-Co/Al₂O₃ catalyst gave the best selectivity for DMF, as a result of a combination of highly dispersed Cu, mixed copper-cobalt oxides, and suitable weak acidic sites. Cu-Co/ZrO₂ had low selectivity for DMF and produced a combination of various over-hydrogenolysis products, including 2,5-dimethyltetrahydrofuran and 5,5-oxybis(methylene)-bis(2-methylfuran), because of the presence of strong acidic sites. The reaction pathways and effects of various operating parameters, namely temperature, H₂ pressure, and time, were studied to enable optimization of the selective conversion of HMF to DMF over the Cu-Co/Al₂O₃ catalyst.

Key words: Hydroxymethylfurfural, Hydrogenation, Hydrogenolysis, Copper-cobalt, Bimetallic, Biofuels

Sanjay Srivastava, G.C.Jadeja, Jigisha Parikh. 载体对其负载的Cu-Co双金属催化剂上5-羟甲基糠醛氢解选择性生成2,5-二甲基呋喃的影响[J]. 催化学报, 2017, 38(4): 699-709.

Sanjay Srivastava, G.C.Jadeja, Jigisha Parikh. Influence of supports for selective production of 2,5-dimethylfuran via bimetallic copper-cobalt catalyzed 5-hydroxymethylfurfural hydrogenolysis[J]. Chinese Journal of Catalysis, 2017, 38(4): 699-709.

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