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.

该提案从根本上反映了旨在减轻可持续现代经济的两个重大障碍的发现和开发研究：重质石油利用和专门针对废木材和农业木质素的可再生生物质“增值”。我们在两个行业（一个是垂死的行业，一个是新兴的行业）寻求颠覆性创新。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气，沥青的最高分子量部分是沥青质，含有大部分耐火材料。重油中的硫、氮和金属化合物几乎不溶于石油基质，污染管道和炼油厂，目前通过热解焦化来去除重油中的杂原子和金属，破坏了约 20-30% 的碳氢化合物价值。石油焦有毒、无价值、对环境持久且生产规模难以想象。这种过程效率低下是不可持续的，但替代的脱沥青方法是初级的，并且比焦化更简单。在 NSERC 的支持下，几十年来没有出现任何“技术经济”的新方法或技术，我们发现了两个昂贵的全新障碍。 - 沥青质和天然木质素无氢加氢脱硫的免费且廉价的途径：（非常）温和的还原电催化和非均相氢转移催化剂沥青质的电催化升级最近从发现科学转向了工艺开发；然而，在本提案中，我们建议研究新型催化剂设计以及沥青质结构和聚集的合成和超分子建模。木质素是赋予木质生物质结构和强度的含氧聚合物，但人们对此知之甚少。木质素没有经济价值。在当今的市场上：热解气化是倒退的，并且在能量上适得其反。迄今为止，尚未报道用于木质素和模型化合物的无氢解聚和脱氧的多相铜催化剂，但尚未优化。纳米催化剂通过氢转移氢解作用，从邻近的醇中脱除氢，并用于裂解将聚合物结合在一起的碳-氧键。木质素的电催化解聚/脱氧仍处于发现阶段，并提供了另一个无机和有机合成。多相催化、反应机制、超分子化学和计算理论：工业现实约束下的发现研究。