Collaborative Research: Rational design of bifunctional catalysts for the conversion of Ievulinic acid to gamma-valerolactone

合作研究：合理设计乙酰丙酸转化为γ-戊内酯的双功能催化剂

• 批准号: 1159863
• 负责人: Andreas Heyden
• 金额: $ 25万
• 依托单位: University South Carolina Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-09-01 至 2016-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1159863&HistoricalAwards=false
• 关键词: Collaborative; Research; Rational; design; bifunctional

The modern petrochemical industry has achieved impressive efficiencies in meeting societaldemands through selective transformations of a few, key building block chemicals. A future self-sustaining biorefining industry will similarly be based on a selected platform of renewable building blocks which may yield transportation fuels or commodity and specialty chemicals. A recent study has identified 10 promising biomass derivatives that have the potential to serve as building blocks for future bio-refineries. Of those, Levulinic Acid (LA) is particularly promising as it can be produced inexpensively and in high yields by sulfuric acid hydrolysis of a variety of lignocellulosic feedstocks. Conversion processes of LA to fuel additives, chemicals, and monomers for plastics and textiles have been demonstrated, but not commercialized. A derived chemical, ?×-valerolactone (GVL), is a promising and extremely flexible intermediate, from which these same numerous desirable end-products can be obtained. Despite a myriad of applications for GVL, its large scale production is not yet established, owing largely to difficulties associated with the purification of its immediate precursor, LA.Professor Andreas Heyden from the University of South Carolina and Professor Jesse Q. Bond from Syracuse University believe these issues have solutions, and have received this NSF award to establish the underlying science that can make feasible the production of the lignocellulosic biomass-derived platform chemical GVL on a commercial scale. In the present state of the art, LA must undergo a costly purification scheme to remove residual sulfuric acid from cellulose hydrolysis prior to conversion to GVL. H2SO4 must be recovered and recycled, in line with a commitment to the long term sustainability of biorefining processes. GVL is sufficiently hydrophobic to allow an energy efficient separation from aqueous sulfuric acid by extraction with a low-boiling acetate followed by facile distillation. A catalytic approach to streamline this step has been proposed. However, the new challenge is the inadequacy of presently available HDO catalysts for processing of unrefined LA. Heyden and Bond propose to use a combined computational and experimental approach to obtain fundamental understanding of the reaction mechanism of the mild, heterogeneously catalyzed hydrodeoxygenation of LA to GVL over Ru/C and RuRe/C catalysts in both aqueous and dilute sulfuric acid solutions, leading to potential improved catalysts and thus making the entire strategy more industrially relevant.The fundamental objective of this project is to create a scientific basis for the rational design of novel heterogeneous catalysts with superior activity, selectivity, and stability for the HDO of LA to GVL in aqueous sulfuric acid. A successful outcome is broadly relevant in aqueous phase processing of lignocellulosic biomass. Further, success of the combined computational and experimental research approach illustrates that such a strategy not only increases our understanding of reaction mechanisms, but also reduces the time and financial resources needed for the design of new heterogeneous catalysts tailored to meet the changing needs of a world with limited resources. The PhD students involved in this project will become experts in the practice and integration of computational and experimental catalysis. Also, the research results will be incorporated into the elective classes ¡§Multiscale Modeling: From Electrons to Chemical Reactors¡¨ being taught by Heyden at the University of South Carolina and ¡§Heterogeneous Catalysis¡¨ being offered by Bond at Syracuse University.

现代石化工业通过选择性地改造一些关键的化学组成部分，在满足社会需求方面取得了令人印象深刻的效率，未来的自我维持的生物炼制行业将同样基于可产生运输燃料或商品的可再生组成部分的选定平台。最近的一项研究发现了 10 种有前景的生物质衍生物，它们有可能成为未来生物精炼厂的基础材料，其中乙酰丙酸 (LA) 特别有前途。通过硫酸水解各种木质纤维素原料，可以廉价且高产地将 LA 转化为燃料添加剂、化学品以及塑料和纺织品单体，但尚未商业化。 GVL）是一种有前途且极其灵活的中间体，从中可以获得同样众多的理想最终产品，尽管 GVL 有无数的应用，但其大规模生产仍在进行中。尚未建立，主要是由于其直接前体的纯化存在困难。南卡罗来纳大学的 Andreas Heyden 教授和雪城大学的 Jesse Q. Bond 教授认为这些问题有解决方案，并获得了 NSF 奖项建立基础科学，使木质纤维素生物质衍生的平台化学品 GVL 的商业规模生产成为可能。在目前的技术水平下，LA 必须进行昂贵的纯化方案以去除残留的硫酸。在转化为 GVL 之前，必须回收和再循环纤维素水解产生的物质，这符合对生物精炼过程长期可持续性的承诺。已经提出了一种简化该步骤的催化方法，但目前可用的 HDO 催化剂不足。 Heyden 和 Bond 提出使用计算和实验相结合的方法来基本了解在 Ru/C 和 RuRe/C 催化剂上 LA 温和非均相催化加氢脱氧为 GVL 的反应机理。硫酸溶液，从而产生潜在的改进催化剂，从而使整个策略更具工业相关性。该项目的根本目标是为新型多相催化剂的合理设计奠定科学基础在硫酸水溶液中将 LA HDO 转化为 GVL 具有优异的活性、选择性和稳定性的催化剂在木质纤维素生物质的水相加工中具有广泛的相关性。此外，计算和实验相结合的研究方法的成功表明了这种方法。该策略不仅增加了我们对反应机制的理解，而且还减少了设计新型多相催化剂所需的时间和财务资源，以满足资源有限的世界不断变化的需求。该项目将成为计算和实验催化实践和整合的专家，研究成果将纳入选修课。 §多尺度建模：从电子到化学反应器¡ ¡ 由海登在南卡罗来纳大学任教，并且 ¡ §多相催化¡由雪城大学邦德提供。