稳定Cu-Zr /介孔SiO2催化剂上乙醇脱氢胺化选择性生产乙腈的研究

IF 9.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Green Chemistry Pub Date : 2025-04-24 DOI:10.1039/d5gc01047k
Xiaomin Zhang , Mo Zhou , Yujia Zhao , Jifeng Pang , Pengfei Wu , Zhen Guo , Mingyuan Zheng
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引用次数: 0

摘要

通过非氧化脱氢胺工艺从乙醇生产乙腈为将生物质衍生的底物转化为高价值化合物提供了一条有吸引力的途径。传统的铜基催化剂在低温(≤330°C)下表现出优异的活性和产物选择性,但存在失活的问题。本文采用尿素辅助沉淀法制备了Cu10-Zr2 /介孔SiO2-UP二元催化剂,用于乙醇脱氢胺制乙腈。在265℃、乙醇WHSV为0.8 h−1、NH3/乙醇摩尔比为9的最佳反应条件下,对乙腈的选择性达到95%,乙醇转化率达到90%以上,反应时间达到116 h以上,是常规反应时间的48倍。系统表征表明,Zr的引入表现出多种功能:(1)增强铜的分散性,(2)防止纳米Cu颗粒的烧结,(3)调节Cu+/Cu0比,(4)改变酸度,(5)调节有机物的吸附-解吸行为。乙醇转化的表观活化能(Ea)从传统单金属催化剂的69.3 kJ mol−1降至Cu-Zr二元催化剂的47.0 kJ mol−1,降低了22.3 kJ mol−1。值得注意的是,该催化剂在将一系列脂肪醇和苯甲醇转化为相应的腈时表现出良好的底物相容性,产率超过85%。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Selective production of acetonitrile via dehydroamination of ethanol over a stable Cu–Zr/meso SiO2 catalyst†
Production of acetonitrile from ethanol via the non-oxidative dehydroamination process provides an attractive route for converting biomass-derived substrates into high-value chemical compounds. Conventional copper-based catalysts exhibit excellent activity and product selectivity at low-temperatures (≤330 °C), but they suffer from the challenge of deactivation. Herein, a binary Cu10–Zr2/meso SiO2-UP catalyst was prepared via a facile urea-assisted precipitation method for ethanol dehydroamination to acetonitrile. Under the optimal reaction condition (265 °C, ethanol WHSV of 0.8 h−1 and NH3/ethanol molar ratio of 9), 95% product selectivity for acetonitrile with over 90% ethanol conversion was realized and maintained for more than 116 h, which was 48-fold longer than that of the conventional counterpart. According to the systematic characterizations, the introduction of Zr exhibited multifunctionality by (1) enhancing the copper species dispersion, (2) preventing the Cu nanoparticle from sintering, (3) adjusting the Cu+/Cu0 ratio, (4) modifying the acidity, and (5) regulating the adsorption–desorption behavior of the organics. The apparent activation energy (Ea) for ethanol conversion dropped by 22.3 kJ mol−1, from 69.3 kJ mol−1 over the conventional monometallic catalyst to 47.0 kJ mol−1 over the as-prepared Cu–Zr binary catalyst. Notably, the catalyst demonstrated excellent substrate compatibility in transforming a series of aliphatic alcohols and benzyl alcohol into the corresponding nitriles with over 85% yields.
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来源期刊
Green Chemistry
Green Chemistry 化学-化学综合
CiteScore
16.10
自引率
7.10%
发文量
677
审稿时长
1.4 months
期刊介绍: Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.
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