Centre for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, KU Leuven, Kasteelpark Arenberg 23, B-3001, Heverlee, Belgium.
Chem Soc Rev. 2014 Nov 21;43(22):7917-53. doi: 10.1039/c4cs00105b.
Increasing demand for renewable feedstock-based chemicals is driving the interest of both academic and industrial research to substitute petrochemicals with renewable chemicals from biomass-derived resources. The search towards novel platform chemicals is challenging and rewarding, but the main research activities are concentrated on finding efficient pathways to produce familiar drop-in chemicals and polymer building blocks. A diversity of industrially important monomers like alkenes, conjugated dienes, unsaturated carboxylic acids and aromatic compounds are thus targeted from renewable feedstock. In this context, on-purpose production of 1,3-butadiene from biomass-derived feedstock is an interesting example as its production is under pressure by uncertainty of the conventional fossil feedstock. Ethanol, obtained via fermentation or (biomass-generated) syngas, can be converted to butadiene, although there is no large commercial activity today. Though practised on a large scale in the beginning of the 20th century, there is a growing worldwide renewed interest in the butadiene-from-ethanol route. An alternative route to produce butadiene from biomass is through direct carbohydrate and gas fermentation or indirectly via the dehydration of butanediols. This review starts with a brief discussion on the different feedstock possibilities to produce butadiene, followed by a comprehensive summary of the current state of knowledge regarding advances and achievements in the field of the chemocatalytic conversion of ethanol and butanediols to butadiene, including thermodynamics and kinetic aspects of the reactions with discussions on the reaction pathways and the type of catalysts developed.
对可再生原料基化学品不断增长的需求，促使学术界和工业界的研究兴趣从石化原料转向生物量衍生资源的可再生化学品。寻找新型平台化学品具有挑战性，但也有回报，主要的研究活动集中在寻找有效途径，以生产类似的、可替代石化产品的化学品和聚合物构建块。因此，人们从可再生原料中定向合成了多种工业上重要的单体，如烯烃、共轭二烯、不饱和羧酸和芳香族化合物。在此背景下，从生物质衍生原料有目的地生产 1,3-丁二烯是一个很有趣的例子，因为其传统石化原料的不确定性使其生产面临压力。通过发酵或（生物质生成）合成气获得的乙醇，可以转化为丁二烯，尽管目前没有大规模的商业活动。虽然在 20 世纪初就已经大规模实践，但全球对从乙醇生产丁二烯的方法的兴趣正在重新增长。另一种从生物质生产丁二烯的方法是通过直接碳水化合物和气体发酵，或者间接通过丁二醇脱水。这篇综述首先简要讨论了生产丁二烯的不同原料的可能性，然后全面总结了目前关于乙醇和丁二醇化学催化转化为丁二烯的研究进展和成果，包括反应的热力学和动力学方面，讨论了反应途径和所开发的催化剂类型。
