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

申请者研究计划的长期目标是开发解决营养/健康和环境问题的食品和非食品加工技术。在这个框架内，他在他的第三次NSERC-Discovery赠款期间从事了利用回收植物油化合作用和多相化合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的研究。他成功地开发了以氯化锌修饰的介孔氧化铝为载体的甲基三氧苯，作为一种新的多相、活性和选择性的催化剂，用于甲醇酸和三油酸酯的自歧化反应。然而，尽管它的活性和选择性很好，但由于在环境相对湿度(在环境温度下为23%)下失活而缺乏稳定性，可能会阻碍其大规模利用，除非应用昂贵的干燥条件。 在未来5年，申请人将继续致力于回收植物油的可持续多相歧化反应，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。 本研究的目的是利用官能化的烯烃歧化反应和一种新型的可调稳定的碳化钼和碳化钨多相催化剂文库，开发出在有价值的平台化学品中转化植物油的经济有效的方法。目标反应是油酸甲酯和甘油三酯的自身歧化反应，以及这些底物与其他一些具有不同油基的官能化烯烃的交叉歧化反应。 该建议的具体目标是：1)金属碳化物催化剂的配方和表征。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，大力提高催化剂的寿命、稳定性和回收利用；2)优化油酸甲酯与一些功能化油基化合物在金属碳化物催化剂上的自和交叉复分解反应操作条件；3)模拟典型植物油的模型甘油三酯的自复化反应。对于特定的目标2)和3)，对于这一新一代复分解催化剂，反应器方面的研究将是重要的。这意味着对吸附/脱附平衡、动力学和反应器模拟和建模的研究；4)回收植物油和商业非食用油在选定的金属碳化物催化剂上的自分解。 该项目将对加拿大油脂行业、整个加拿大农业企业以及加拿大化学工业产生重大影响。利用这种集成的加工技术(催化剂和反应)，各种官能团可以被加入到生物基材料中。

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.