Abstract:

Biomass ethanol is the building block for producing a variety of high value-added chemicals (e.g. acetaldehyde, olefins, butanol and high carbon alcohols, aromatic alcohols/aldehydes, etc.) through catalytic dehydrogenation, dehydration, aldol condensation, cyclization, etc. The catalytic conversion of biomass ethanol to high value-added chemicals is a green route with low carbon emission and high atomic economy. Due to the complexity of the ethanol reaction network, the main concern for this pathway is the synergy of different catalytic active sites with matched elemental reaction rates. This article reviews the research progress of heterogeneous catalytic ethanol conversion to high value-added chemicals according to the types of products based on the understanding of the active center, reaction pathway and reaction mechanism. For the catalyst system and reaction mechanism, the synergetic modulation of multi-active center and the structure-performance relationship are summarized. The regulation mechanism of the product distribution is clarified. It is also pointed out that the preparation of higher value-added C₆₊ alcohols and aromatic oxygenate from ethanol is the most promising research in the future. From the industrial application viewpoint, there is an urgent need to develop integrated reaction-separation technology for ethanol conversion and utilization.

Key words: ethanol, catalysis, multiphase reaction, acetaldehyde, butadiene, high-carbon alcohol, aromatic alcoho

摘要：

生物质乙醇可作为平台分子催化转化制备高附加值化学品，是一条低碳环保的绿色路线。乙醇性质活泼，经催化脱氢、脱水、羟醛缩合、环化等可制备多种高附加值化学品（如乙醛、烯烃、丁醇、高碳醇、芳香醇/醛等）。但乙醇催化转化反应网络复杂，实现乙醇定向转化的核心是催化剂上不同活性中心的高效协同，以及多步基元反应的速率匹配。本文通过对乙醇转化活性中心、反应路径和反应机理的认识，根据反应产物的种类，系统综述了多相催化乙醇制备高值化学品的研究进展。针对乙醇定向转化的催化剂体系及反应机理，概述了多活性中心协同调变机制和催化剂活性中心与乙醇转化性能的构效关系，阐明了乙醇转化产物分布的调控机理。其中，由乙醇出发制备C₆₊高碳醇和芳香醇/醛等高值含氧化合物可能是未来乙醇转化利用的研究重点，从工程应用角度，亟需发展乙醇转化利用的反应分离一体化技术。

关键词: 乙醇, 催化, 多相反应, 乙醛, 丁二烯, 高碳醇, 芳香醇