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

这个小企业技术转让（STTR）第一阶段项目的更广泛的影响/商业潜力是将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求一种生物基的低碳替代品，经济学是主要障碍。该项目的高产量乳酸转丙烯酸技术将有助于玉米利用行业的发展，并为美国农村地区提供高薪工作，以及在全球市场上的经济竞争力。据估计，每一家将糖发酵的乳酸转化为直接、低碳、可再生丙烯酸的工厂都能为一个拥有重要生物基糖作物的县带来1200万美元的经济活动（例如，玉米、甜菜、甘蔗）。将目前的石化丙烯酸转化为生物基原料需要大约250个工厂。STTR第一阶段项目建议使用催化剂创新（包括阳离子交换沸石的工程胺处理）来利用高醇含量的原料。该催化剂已被证明优于许多以前使用的催化剂，在乳酸的催化脱水过程中，丙烯酸产物的产率为90%。迄今为止，本领域技术人员已经研究了含有浓度为10- 40%的乳酸甲酯或乳酸的水溶液的饲料。甲醇尚未用作浓度大于5%的共进料，因此本项目将研究更高浓度的醇（5%-80%，使用甲醇或乙醇）。 该项目将使用甲醇和乙醇，因为醇的大小可能会改变活性部位的反应性和/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的两个关注领域，并确定了在竞争性吸附条件下乙醇和乳酸的相对脱水速率，以提供反应器缩放所需的基础信息。该研究还增加了丙烯酸烷基酯形成的百分比，迫使气相酯化丙烯酸与酒精走向completen.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

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.