Sustainable Heterogeneous Metathesis of Recycled Vegetable and Non-edible oils: A Green Route to Value-Added Platform Chemical Synthesis

申请人研究计划的长期目标是开发食品和非食品加工技术，解决营养/健康和环境问题。在此框架内，他在第三次NSERC发现资助期间继续研究使用回收植物油复分解和非均相复分解催化剂生产用于高性能生物塑料生产的功能化聚合物构建块。他成功地开发了负载在ZnCl 2改性的介孔Al 2 O3上的甲基三氧化铼，作为一种新的多相活性和选择性催化剂，用于羟甲基丙烷和三油酸甘油酯自复分解。然而，即使其活性和选择性优异，由于在环境相对湿度（在环境温度下> 23%）下失活，其缺乏稳定性可能妨碍其大规模利用，除非应用昂贵的干燥条件。 在接下来的5年里，申请人打算继续致力于回收植物油的可持续多相复分解，并开发用于高附加值平台化学合成的高活性化学选择性和更稳定的绿色催化剂。 本研究提案的目的是开发经济上有利可图的工艺，用于植物油转化为有价值的平台化学品，使用官能化烯烃复分解和一种新的可调和稳定的钼和碳化钨基非均相催化剂库。油酸甲酯和甘油三酯的自复分解以及这些底物与具有不同油基的许多其他官能化烯烃的交叉复分解将是目标反应。 本课题的具体目标是：1）金属碳化物催化剂的制备与表征。这意味着通过开发新一代活性和化学选择性金属（Mo和W）碳化物来提高催化剂寿命、稳定性和再循环的巨大努力; 2）优化油酸甲酯在基于金属碳化物的催化剂上与许多官能化油烯基化合物的自复分解和交叉复分解的反应操作条件; 3）模拟典型植物油的模型甘油三酯的自复分解。对于具体目标2）和3），反应器方面对于研究这种新一代复分解催化剂将是重要的。这意味着对吸附/解吸平衡、动力学和反应器模拟和建模的研究; 4）在选定的金属碳化物催化剂上回收植物油和商业非食用油的自复分解。 该项目将产生的好处是非常重要的加拿大油脂工业，加拿大农业企业整体以及加拿大化学工业。使用这种集成处理技术（催化剂和反应），可以将各种官能团引入生物基材料中。

The long-term goal of the applicant’s research program is to develop food and non-food processing technologies addressing nutritional/health and environmental concerns. Within this framework, he pursued during his 3rd NSERC-Discovery grant, research on the production of functionalized polymer building blocks for high performance bioplastic production using recycled vegetable oil metathesis and heterogeneous metathesis catalysts. He successfully developed methyltrioxorhenium supported on ZnCl2-modified mesoporous Al2O3 as a new heterogeneous active and selective catalyst for methyloeate and triolein self-metathesis. However, even though its activity and selectivity were excellent, its lack of stability due to deactivation at ambiant relative humidity (> 23 % at ambiant temperature) can hamper its large utilization, unless costly dry conditions were applied. For the 5 next years, the applicant intends to continue focusing his efforts in sustainable heterogeneous metathesis of recycled vegetable oils and developing highly active chemoselective and more stable green catalysts for high value-added platform chemical synthesis. The aim of this research proposal is to develop economically profitable processes for the vegetable oil transformation in valuable platform chemicals using functionalized olefin metathesis and a novel library of tunable and stable molybdenum and tungsten carbide-based heterogeneous catalysts. The self-metathesis of methyloleate and triglycerides as well as the cross-metathesis of these substrates with a number of other functionalized olefins with different oleyl groups will be the targeted reactions. The specific objectives of the proposal are: 1) Metal carbide catalysts formulation and characterization. This implies drastic efforts to improve catalysts life span, stability and recycling by developing a new generation of active and chemoselective metal (Mo and W) carbides; 2) Optimization of the reaction operating conditions for methyloleate self- and cross-metathesis with a number of functionalized oleyl compounds over metal carbide-based catalysts; 3) Self-metathesis of model triglycerides simulating typical vegetable oils. For the specific objectives 2) and 3), the reactor aspects will be important to study for this new generation of metathesis catalysts. This implies investigations on adsorption/desorption equilibria, kinetics and reactor simulation and modelling; 4) Self-metathesis of recycled vegetable oils and commercial non-edible oils over selected metal-carbide catalysts. The benefits that would accrue from this project are highly significant to the Canadian fats and oils industry, the Canadian Agri-business overall as well as the Canadian chemical industry. Using this integrated processing technology (catalysts and reactions), a variety of functional groups can be incorporated into the bio-based materials.