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采用溶胶-凝胶法制备的 Ni/AlO-TiO-ZrO 负载型催化剂催化 5-羟甲基糠醛加氢制备 2,5-二甲基呋喃:供氢剂的影响。

2,5-Dimethylfuran Production by Catalytic Hydrogenation of 5-Hydroxymethylfurfural Using Ni Supported on AlO-TiO-ZrO Prepared by Sol-Gel Method: The Effect of Hydrogen Donors.

机构信息

Centro de Investigación de Ciencia y Tecnología Aplicada de Tabasco (CICTAT), Laboratorio de Nanomateriales Catalíticos Aplicados al Desarrollo de Fuentes de Energía y Remediación Ambiental, División Académica de Ciencias Básicas (DACB), Universidad Juárez Autónoma de Tabasco, Km. 1 Carretera Cunduacán-Jalpa de Méndez, Cunduacán 86690, Mexico.

Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Km. 107 Carretera Tijuana-Ensenada, Apdo. Postal 14, C.P., Ensenada 22800, Mexico.

出版信息

Molecules. 2022 Jun 29;27(13):4187. doi: 10.3390/molecules27134187.

Abstract

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on AlO-TiO-ZrO (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni, Ni/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Py, H-TPD, CO-TPD, H-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using H NMR. It was found that the NiNiO/ATZ3 catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar).

摘要

5-羟甲基糠醛(5-HMF)已被美国能源部描述为源自生物质的 12 种关键平台分子之一,其加氢反应可生成 2,5-二甲基呋喃(2,5-DMF)等多功能液体生物燃料。在 AlO-TiO-ZrO(ATZ)混合氧化物负载的镍催化剂上,使用异丙醇和甲酸(FA)作为供氢体,对 5-HMF 催化加氢制备 2,5-DMF 进行了深入研究,以寻找最佳反应条件和供氢体。考察了金属含量(wt%)、Ni 粒径(nm)、Ni 物种、Ni/NiO 和 NiO 物种、金属活性位和酸位、供氢体(异丙醇和甲酸)等因素对催化剂的影响。采用 N 物理吸附、XRD、Raman、DRS UV-Vis、FT-IR、SEM、FT-IR Py、H-TPD、CO-TPD、H-TPR、TEM 和 XPS 等多种物理化学方法对材料的结构特征进行了研究。使用 H NMR 对第二代 2,5-DMF 生物燃料和 5-HMF 转化副产物进行了分析和阐明。结果表明,浸渍法(WI)合成的 NiNiO/ATZ3 催化剂产生了良好的协同作用,在 210℃、20 bar 氩气压力和甲酸作为供氢体的条件下,反应 24 h 后,对 5-HMF 催化加氢生成 2,5-DMF 的效果最好。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3115/9268021/256b56bfe023/molecules-27-04187-sch001.jpg

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