Metathesis of ethylene with 2-butenes over WOx-, MoOx- and ReOx-based catalysts: understanding the fundamentals of catalyst functioning

乙烯与 2-丁烯在 WOx、MoOx 和 ReOx 基催化剂上的复分解：了解催化剂功能的基本原理

• 批准号: 414641548
• 负责人: Dr. Tatiana Otroshchenko
• 金额: --
• 依托单位: Leibniz-Institut für Katalyse e. V. an der Universität Rostock (LIKAT)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/414641548?language=en
• 关键词: Metathesis; ethylene; butenes; over; WOx

The metathesis of ethylene with 2-butenes to propene is a large-scale process, in which WOx- (and rarely MoOx- and ReOx-) based catalysts together with a co-catalyst (MgO) are applied. Despite the fact that such reaction is thoroughly investigated by academia and industry, there is still a lot of fundamental questions concerning catalyst functioning. Their answering will provide a basis for catalyst design and for identification of reaction conditions required for optimal propene formation. To close such gap, the current project is intended i) to provide fundamentals for the development of active and stable catalysts for the metathesis of ethylene with 2-butenes; ii) to identify optimal conditions of catalyst operation; and iii) to establish structure-reactivity relationships. In order to achieve the project goals, a series of WOx-, MoOx- and ReOx-based catalysts with a well-defined MOx (M = W, Mo or Re) structure will be synthesized and thoroughly characterized by complementary techniques. The catalysts will be tested in metathesis of ethylene with trans-2-butene under steady-state and transient conditions. The influence of different factors (e.g. dispersion of MOx species, the kind of support material, the presence of reducing agent in metathesis feed or metathesis-inactive co-catalysts with these both being used as promoters, catalyst pre-treatment) on the amount of in situ formed active species, which are metal-carbenes, is to be elucidated. Operando tests (IR, Raman, UV-vis) will be performed in order to monitor the changes in catalyst composition and structure during pre-treatment and metathesis reaction. The obtained fundamental insights will be applied for a rational design of improved catalysts as well as general guidelines for efficient catalyst operation including the presence of gas-phase and solid promoters.

乙烯与2-丁烯到丙烯的复分解是大规模方法，其中应用基于WOx-（和很少的MoOx-和ReOx-）的催化剂以及助催化剂（MgO）。尽管学术界和工业界对这种反应进行了深入的研究，但仍然存在许多关于催化剂功能的基本问题。他们的回答将为催化剂设计和确定最佳丙烯形成所需的反应条件提供基础。为了缩小这一差距，目前的项目旨在i）为开发用于乙烯与2-丁烯复分解的活性和稳定的催化剂提供基础; ii）确定催化剂操作的最佳条件; iii）建立结构-反应性关系。为了实现项目目标，将合成一系列具有明确MOx（M = W，Mo或Re）结构的WOx，MoOx和ReOx基催化剂，并通过互补技术进行全面表征。将在稳态和瞬态条件下在乙烯与反式-2-丁烯的复分解中测试催化剂。阐明不同因素（例如MOx物质的分散、载体材料的种类、复分解进料中还原剂或复分解非活性助催化剂的存在，其中这两者都用作促进剂、催化剂预处理）对原位形成的活性物质（其为金属-卡宾）的量的影响。将进行操作试验（IR、拉曼、UV-vis），以监测预处理和复分解反应期间催化剂组成和结构的变化。所获得的基本见解将适用于改进的催化剂的合理设计以及有效的催化剂操作，包括气相和固体促进剂的存在下的一般准则。