(TSE03-C)Alkane production from renewable biomass by aqueous-phase catalytic reforming: A combined experimental and theoretical approach

该项目将解决利用新发现的低温水相重整工艺从生物质衍生的含氧烃催化生产烷烃的问题。这一新工艺为利用可再生生物质资源生产烷烃提供了一条途径。这项创新的核心是通过含氧碳氢化合物与液态水在低温(近200摄氏度)下反应生产富含碳氢化合物的燃料气。其主要优点包括：(1)在不挥发水的情况下生成烷烃，这是一种主要的节能措施；(2)在有利于水-气变换反应的温度下运行，使在单个化学反应器中生成低CO含量的高质量燃料气成为可能。这一过程为现代高效内燃机(ICE)提供了一种生物可再生燃料的战略。可再生烷烃与高效冰的结合为可持续生产温室气体中性的机械和电力能源提供了一种很有前途的方法，因为重整过程排放的二氧化碳被下一年的生物质生长所消耗。这种生产烷烃的新工艺的潜在技术影响是巨大的，使美国经济对进口化石燃料的依赖大大减少。目前被发现的用于水相重整工艺生产烷烃的最佳催化剂是以贵金属铂为基础的。将进一步研究开发新一代催化剂，以提供成本效益高的方法，利用水相重整过程转化从生物质蒸气中提取的反应物来生成烷烃。将研究添加剂以改善铂基催化剂的性能、成本和效率。反应条件(如温度、压力、进料浓度、溶液pH)也将改变，以控制产物的分布，并将确定长时间水蒸气的催化性能。这些研究将依赖于：(1)催化剂候选的高通量筛选，(2)最有希望的候选催化剂的详细催化反应动力学研究，(3)最有希望的催化材料的光谱和表征研究，以及(4)过渡金属上C-C，C-O，C-H和O-H键活化的系统第一性原理研究。

This project will address the catalytic production of alkanes from biomass-derived oxygenated hydrocarbons utilizing a newly discovered low-temperature aqueous-phase reforming process. This new process provides a route for generation of alkanes from renewable biomass resources. The core of the innovation is the production of hydrocarbon-rich fuel-gas by reactions of oxygenated hydrocarbons with liquid water at low temperatures (near 200 C). The main advantages include: (1) generation of alkanes without the need to volatilize water, which represents a major energy saving, and (2) operation at temperatures where the water-gas shift reaction is favorable, making it possible to generate high-quality fuel-gas with low amounts of CO in a single chemical reactor. The process provides a strategy for delivering a biorenewable fuel for modern, highly efficient internal combustion engines (ICEs). The combination of renewable alkanes with efficient ICEs provides a promising method for sustainable generation of mechanical and electrical energy that is green house gas neutral, since the CO2 emitted from the reforming process is consumed by the next year's growth of biomass. The potential technological impact of this new process for the production of alkanes is substantial, leading to a considerable decrease in the dependence of the US economy on imported fossil fuels.The best catalysts identified at present for the generation of alkanes by the aqueous-phase reforming process are based on platinum, which is an expensive metal. Further research will be conducted to develop a new generation of catalysts to provide cost-effective methods to generate alkanes using the aqueous-phase reforming process to convert reactants extracted from biomass streams. Additives will be investigated to improve the performance, cost, and efficiency of Pt-based catalysts. The reaction conditions (such as temperature, pressure, feed concentrations, solution pH) will also be varied to control the product distribution, and catalytic performance with respect to long times on-steam will be determined. The investigations will rely on: (1) high throughput screening of catalyst candidates, (2) detailed catalytic reaction kinetics studies of the most promising catalyst candidates, (3) spectroscopic and characterization studies of the most promising catalytic materials, and (4) systematic first-principles studies for C-C, C-O, C-H, and O-H bond activation on transition metals.