STTR Phase I: Production of aromatic commodity chemicals via the coumalic acid platform using the catalyzed Diels-­‐Alder reaction in a continuous flow reactor

这一小型企业技术转让第一阶段项目的更广泛影响/商业潜力是加快利用作物原料制造生物基芳烃化学品，如对苯二甲酸和苯甲酸，目前这两种化学品的全球市场价值分别为600亿美元和2亿美元。该项目专注于苯甲酸(从食品添加剂到增塑剂的应用)作为第一个商业目标，以获得市场立足点并开发这项技术。这项技术将为苯甲酸提供一种生物来源，目前苯甲酸几乎完全由石化产品甲苯的氧化产生。SusTerea Biorenewables LLC位于美国生物质生产的中心爱荷华州，可以影响农村经济，将乙醇以外的作物材料的利用扩大到生物基化学品的生产。这一第一阶段研究项目的技术目标是开发基于生物的香豆酸平台，用于生产一系列具有工业重要性的芳香族分子。该项目的技术基础始于美国国家科学基金会工程研究中心生物可再生化学品中心(CBiRC)的研究人员确定了将工业优化的发酵产品(苹果酸)转化为香豆酸的化学催化途径，并发现香豆酸可用于生产一系列芳香化合物，如苯甲酸、对苯二甲酸和对苯二甲酸二甲酯。因此，在蓬勃发展的生物可再生化学工业中，香豆酸具有成为平台化学机会的潜力。首先，将优化使用工业规模连续流动反应器的反应条件，包括温度、压力和溶剂。第二，将探索取代贵金属的新催化剂，用于关键的芳构化步骤。第三，这些实验数据将被用来构建初步的工艺设计和技术经济模型，以开发可扩展的生产技术。

The broader impact/commercial potential of this Small Business Technology Transfer Phase I project is the accelerated utilization of crop materials for the manufacture of biobased aromatic chemicals such as terephthalic acid and benzoic acid, which currently have global market value of $60 billion and $200 million, respectfully. This project focusses on benzoic acid (applications ranging from food additives to plasticizers) as the first commercial target to gain a market foothold and develop this technology. This technology will provide a biobased source for benzoic acid, which is currently produced almost exclusively from the oxidation of petrochemical toluene. Situated in Iowa, the epicenter of biomass production in the United States, SusTerea Biorenewables LLC can impact the rural economy, expand the utilization of crop materials beyond ethanol into the production of biobased chemicals. The technical objectives in this Phase I research project is development of the biobased coumalic acid platform, for producing an array of industrially important aromatic molecules. The technological basis for the project began with the identification by researcehers at the NSF Engineering Research Center, Center for Biorenewable Chemicals (CBiRC) of a chemical catalysis pathway to transform an industrially optimized fermentation product (malic acid) into coumalic acid and the discovery that coumalic acid could be used to produce an array of aromatics such as benzoic acid, terephthalic acid, and dimethyl terephthalate. Thus, coumalic acid has the potential to become a platform chemical opportunity in the burgeoning biorenewable chemical industry. First, the reaction conditions including temperature, pressure and solvent using an industrially relevant bench scale continuous flow reactor will be optimized. Second, new catalysts to substitute noble metals will be explored for the key aromatization step. Third, this experimental data will be used to construct a preliminary process design and a techno- economic model towards developing a scalable production technology.