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.

这项提案的基本和发展旨在减轻对可持续经济的重要性：大量石油利用和可再生生物量“专门针对沃斯特木材和农业木质素。 - 沥青的高温和压力在沥青中销毁约20-30％的沥青，以将燃料转换为燃料和石化方法。通往无氢氢化的沥青和天然木质素的途径：在（非常）轻度的条件下还原的电载氢转移催化剂。目的。沥青结构的设计，合成和超分子模型，几乎没有木质素是氧化聚合物的结构和强度。纳米构体通过氢化，从邻近的氢中剥离氢，并将其固定在碳氧化阶段的碳中和有机综合，反应机制，超分子化学和计算理论：发现研究的发现研究的限制。