Reaction-Separation Processes for Production of Hydroxymethylfurfural from Fructose using Molecular Sieves

生物质作为碳中性化学和燃料来源的实际开发受到适合于亲水性、氧官能化和热不稳定的生物质原料的化学转化的工艺和反应工程技术的发展的限制。这项研究旨在同时利用沸石材料的择形催化性能和在催化膜反应器中实施的选择性分离，从而实现糖单体转化的低温催化和分离过程，特别是将果糖脱水转化为羟甲基呋喃(HMF)。该项目基于初步数据，表明利用沸石分子筛膜可以选择性地从果糖中分离出HMF，并试图将之前的工作从合成高选择性、高渗透性的烃分离膜扩展到集成反应分离系统和多功能生物质衍生原料。该项目的智力价值汇集了Tasatsis(沸石膜)、Bhan(沸石催化)和Daoutidis(工艺设计和控制)研究小组的互补和不同的经验，以开发以生物质为原料的新的反应分离工艺技术。具体地说，联合PIs计划：(I)使用稳态和化学/同位素瞬时实验研究来确定果糖脱水的动力学、机理和现场要求，以便为工艺设计提供对反应速率的严格描述；(Ii)研究分子筛膜分离果糖衍生的含氧官能化分子的潜力，并定量评估吸附和传输现象对HMF生产的速率和选择性的影响；以及(Iii)设计和优化基于(I)和(Ii)以及在过程工程水平上将这种方法与文献中提出的其他反应-吸附和反应-萃取两相系统进行比较。研究包括反应系统中传输和吸附现象与动力学的相互作用，以设计适合生物质原料特定分子结构的集成低温反应-分离系统，并将化学反应工程方法扩展到过程强化，包括生物质加工。催化剂开发、用于分离的新材料和高能效的反应-提纯工艺集成相结合，有可能促进这一转变。在这方面，这项研究将产生更广泛的方法学影响，并可能刺激开发与生物精炼过程相关的其他问题的解决方案。联合绩效指标将把这项工作的内容作为案例研究纳入以反应工程和分离为重点的本科生/研究生高级课程，并纳入将在因特网上提供的教学单元。将鼓励本科生从事该项目的各个方面的工作，并将重点放在招聘工作上，以确保联合绩效指标研究小组内继续保持多样性。

0855863TsapatsisThe practical exploitation of biomass as a carbon-neutral source of chemicals and fuels is limited by the development of process and reaction engineering technology suited for the chemical transformation of hydrophilic, oxygen-functionalized and thermally unstable biomass feedstock. This research seeks to simultaneously harness the shape selective catalytic properties of zeolitic materials and selective separations for implementation in catalytic membrane reactors that will enable low temperature catalytic and separation processes for conversion of sugar monomers, specifically for dehydration of fructose to hydroxymethylfurfural (HMF). It is predicated upon preliminary data that show HMF can be selectively separated from fructose using zeolite membranes and seeks to extend previous work from the PI on the synthesis of high-selectivity, high-permeability membranes for hydrocarbon separations to integrated reaction-separation systems and to polyfunctional biomass-derived feedstock.Intellectual Merit The project brings together the complementary and diverse experience of the Tsapatsis (zeolitic membranes), Bhan (zeolite catalysis) and Daoutidis (process design and control) research groups to develop new reaction-separation process technologies using biomass as feedstock. Specifically, the co-PIs plan to:(i) Determine the kinetics, mechanism and site requirements for the dehydration of fructose using steady state and chemical/isotopic transient experimental studies to provide a rigorous description of reaction rates for process design,(ii) Investigate the potential of zeolite-membranes to separate fructose-derived oxygenfunctionalized molecules and quantitatively assess the effect of adsorption and transport phenomena on the rate and selectivity of HMF production, and(iii) Design and optimize an integrated reaction-separation system based on (i) and (ii) and also, compare and contrast this methodology at a process engineering level with other reactionadsorption and reaction-extraction biphasic systems proposed in the literature.The research encompasses the interaction of transport and adsorption phenomena with kinetics in reaction systems for the design of integrated low-temperature reaction-separation systems adapted for the specific molecular structure of biomass feedstock and extends chemical reaction engineering approaches to process intensification to include biomass processing.Broader Impact Transforming traditional chemical processing and production is one of the challenges the global society faces to ensure a sustainable future. Combination of catalyst development, new materials for separations and energy efficient reaction-purification process integration has the potential to contribute to this transformation. In this respect, the research will have broader methodological impact and may stimulate the development of solutions for other problems related to biorefinery processes. The co-PIs will incorporate elements of this work as case studies in an advanced undergraduate/graduate course that focuses on reaction engineering and separations and in teaching-modules that will be made available on the internet. Undergraduate students will be encouraged to work on aspects of the project and emphasis will be given in recruiting efforts to assure continued diversity within the co-PIs research groups.