Hydrogen-free hydrogenolysis of strong C-S, C-O, and C-N bonds

强 C-S、C-O 和 C-N 键的无氢氢解

• 批准号: RGPIN-2022-03282
• 负责人: Stryker, Jeffrey
• 金额: $ 3.5万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748113
• 关键词: Hydrogen; free; hydrogenolysis; strong; bonds

This proposal reflects fundamental discovery and development research directed toward mitigating two significant impediments to a sustainable modern economy: heavy petroleum utilization and renewable biomass "valourization" specifically targeting waste wood and agricultural lignin. We seek disruptive innovation in both industries, one moribund, one emergent. Bitumen refining is capital- and energy-intensive, consuming hydrogen at very high temperatures and pressures. The highest molecular weight fraction of bitumen, the asphaltenes, contain most of the refractory sulfur, nitrogen, and metal compounds in heavy oil. Asphaltenes are barely soluble in the petroleum matrix, fouling pipelines and refineries. Removing heteroatoms and metals from heavy oil is currently accomplished by pyrolytic coking, destroying ~20-30% of the hydrocarbon value in bitumen to convert the remainder into fuels and petrochemicals. Petroleum coke is toxic, valueless, environmentally persistent, and produced on unimaginable scale. The inefficiency of this process is unsustainable, but alternative de-asphalting methods are rudimentary and more expensive than coking. No "techno-economic" new methods or technologies have emerged have appeared in decades. Under NSERC support, we have discovered two radically new, obstacle-free, and inexpensive pathways to hydrogen-free hydrodesulfurization of the asphaltenes and native lignin: reductive electrocatalysis and heterogeneous hydrogen-transfer catalysts under (very) mild conditions. Electrocatalytic upgrading of bitumen asphaltenes recently crossed from discovery science to process development;  funding from other sources is now used for that purpose. In this proposal, however, we propose to investigate novel catalyst design and synthetic and supramolecular modelling of asphaltene structures and aggregation, about which little is known.         Lignin is the oxygenated polymer that gives woody biomass its structure and strength. Forestry and agricultural waste-woods have no economic value in today's market: pyrolytic gasification is regressive and energetically counterproductive. No non-destructive processes for lignin depolymerization have been reported - until now. Heterogeneous copper catalysts for hydrogen-free depolymerization and deoxygenation of lignin and model compounds have been demonstrated, albeit not optimized.  The nanocatalysts function by hydrogen-transfer hydrogenolysis, stripping hydrogen from a neighbouring alcohol and it using to cleave the carbon-oxygen bond that holds the polymer together. The products are simple aromatic alcohols. No complex bio-oils or gases. Electrocatalytic depolymerization/deoxygenation of lignin remains at the discovery stage, and provides another of this proposal.   Inorganic and organic synthesis, heterogeneous catalysis, reaction mechanisms, supramolecular chemistry, and computational theory:  discovery research witin the constraints of industrial reality.

该提案反映了旨在减轻可持续现代经济的两个重大障碍的基本发现和发展研究：大量石油利用和可再生生物量“ valourization”专门针对废木和农业木质素。我们在这两个行业中寻求破坏性的创新，一个垂死，一个新兴的创新。沥青精炼是资本和能源密集型的，在非常高的温度和压力下消耗氢。沥青的最高分子量分数，沥青质，含有重油中的大部分难治性硫，氮和金属化合物。石油基质，污染管道和炼油厂的沥青质几乎没有固体。目前通过热溶解焦油来清除重油的杂原子和金属，破坏了沥青中约20-30％的碳氢化合物价值，以将其余部分转化为燃料和石化化学物质。石油可乐是有毒，毫无价值的，环境持久的，并且以难以想象的规模生产。此过程的效率低下是不可持续的，但是替代截面方法是基本的，比焦化更昂贵。几十年来，没有出现“技术经济”新方法或技术。在NSERC支持下，我们发现了两种彻底的，无障碍且廉价的途径，用于沥青质和天然木质素的无氢氢硫化：还原性电催化和异质氢转移催化剂在（非常）的温和条件下。沥青沥青质的电催化升级最近从发现科学到过程开发；现在，来自其他来源的资金用于此目的。然而，在该提案中，我们建议研究沥青质结构和聚集的新型催化剂设计以及合成和超分子建模，这几乎没有知名度。木质素是含氧聚合物，可为木质生物量提供其结构和强度。林业和农业废物在当今市场上没有经济价值：热解气化是回归性的，有效的适得其反。到目前为止，还没有报道木质素沉积的无损过程。已经证明了用于木质素和模型化合物的无氢沉积和脱氧的异质铜催化剂，尽管未进行优化。纳米催化剂通过氢转移氢解，从邻近酒精中剥离氢，并用于清除将聚合物凝聚在一起的碳氧键。这些产品是简单的芳香醇。没有复杂的生物油或气体。木质素的电催化沉积/脱氧保留在发现阶段，并提供了另一种建议。无机和有机综合，异质催化，反应机制，超分子化学和计算理论：发现研究见证了工业现实的限制。