STTR Phase I: Effect of Alcohol Concentration on Lactic to Acrylic Selectivity and Deactivation Rate over Na-FAU Zeolite Catalysts

这个小企业技术转移（STTR）第一阶段项目的更广泛的影响/商业潜力是将一种生产低碳、生物基丙烯酸和丙烯酸酯的工艺商业化，用于油漆、涂料、粘合剂和高吸水性聚合物市场。几十年来，这个价值100亿美元的市场一直在寻找一种基于生物的低碳替代品，但经济是主要障碍。该项目的高产量乳酸制丙烯酸技术将有助于发展玉米利用产业，为美国农村提供高薪就业机会，并在全球市场上提高经济竞争力。据估计，每一个将糖发酵的乳酸转化为低碳、可再生丙烯酸的工厂，将为一个拥有重要生物基糖作物（如玉米、甜菜、甘蔗）的县带来1200万美元的经济活动。在这种规模上，大约需要250个工厂来将今天的石化丙烯酸转化为生物基来源。该STTR一期项目建议使用创新催化剂，包括对阳离子交换沸石进行工程胺处理，以利用高酒精含量的原料。该催化剂已被证明优于许多以前使用的催化剂，在催化乳酸脱水过程中丙烯酸产品的收率为90%。到目前为止，实地人员已经研究了含有乳酸甲酯水溶液或乳酸浓度在10-40%之间的饲料。甲醇作为共饲料的浓度未超过5%，因此本项目将研究更高浓度的醇（5%-80%，使用甲醇或乙醇）。该项目将同时使用甲醇和乙醇，因为酒精的大小可能会改变活性位点的反应活性和/或改变酯化与酸性丙烯酸酯产品的平衡。这些实验解决了该技术商业化中关注的两个领域，并确定了竞争吸附条件下乙醇和乳酸的相对脱水速率，为反应器缩放提供所需的基础信息。拟议的研究还增加了通过迫使丙烯酸与醇的气相酯化完成而形成的丙烯酸烷基酯的百分比。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

The broader impact/commercial potential of this Small Business Technology Transfer (STTR) Phase I project is to commercialize a process to produce low carbon, bio-based acrylic acid and acrylates for paints, coatings, adhesives, and superabsorbent polymer markets. This $10 billion market has been seeking a bio-based, low-carbon alternative for decades, with economics serving as the major barrier. This project’s high yield lactic-to-acrylic technology will help grow the corn utilization industry and provide high paying jobs across rural America as well as economic competitiveness in global markets. Every plant constructed to convert lactic acid fermented from sugar into drop-in, low-carbon, renewable acrylic acid is estimated to bring $12 million in economic activity to a county with significant bio-based sugar crops (e.g., corn, beets, cane). Approximately 250 plants are needed at this scale to convert today’s petrochemical acrylic acid to a bio-based source.This STTR Phase I project proposes to utilize high alcohol content feedstocks using catalyst innovation comprising engineered amine treatment of cation-exchanged zeolites. The catalyst has been shown to outperform numerous previously-utilized catalysts with 90% yields of acrylic products during catalyzed dehydration of lactic acid. So far, those in the field have investigated feeds containing aqueous solutions of methyl lactate or lactic acid in concentrations from 10-40%. Methanol has not been used as a co-feed in concentrations greater than 5%, therefore this project will investigate higher concentrations of alcohols (5%-80%, using methanol or ethanol). The project will use both methanol and ethanol as the alcohol size is likely to alter active site reactivity and/or shift the equilibrium of esterified versus acidic acrylate products. These experiments address two areas of concern in the commercialization of the technology and determine the relative dehydration rates of ethanol and lactic acid under competitive adsorption conditions to provide foundational information required for reactor scaling. The proposed research also increases the percentage of alkyl acrylates formed by forcing the gas phase esterification of acrylic acid with alcohol towards completion.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.