CO Hydrogenation to Long-chain Terminal Alcohols and Aldehydes: A Combined Approach by Transient Kinetics and Theoretical Modeling

摘要标题：CO加氢制长链末端醇和醛：瞬态动力学和理论模拟相结合的方法均相催化剂广泛应用于工业化学过程中，用于生产长链醇和醛，然后将其用作其他化学过程的原料。该生产方法具有几个缺点，因为它涉及几个工艺步骤，并且因为催化剂中昂贵的贵金属必须小心回收。生产长链醇的另一种方法是通过使用非均相催化剂，该非均相催化剂将氢加入一氧化碳中，使用由地球上丰富的金属如钴或铁制成的催化剂。这种技术在石油化学工业中起着重要作用，因为石油化学工业的兴趣在于生产长链烃。当涉及到长链含氧烃的生产时，应用较少。虽然已知不同的金属具有不同的催化性能，但合理设计催化剂，使其能够产生最有用的产物，同时产生最少的副产物，仍然是工业实验室的主要挑战。然而，最近的研究结果表明，多相催化路线实际上可以是一个“一步，一锅”的过程，没有宝贵的贵金属损失的风险。该奖项授予华盛顿州立大学催化中心的Norbert Kruse和Jean-Sabin麦克尤恩教授，旨在为设计具有上级催化活性和性能的催化剂提供必要的科学依据，用于从一氧化碳生产长链含氧化合物。这一过程的影响在缩小传统上基于化石燃料的化学产品与可能基于一氧化碳的化学产品之间的成本差距方面尤为重要。PI还将与菲利普斯66公司（位于华盛顿州炼油厂芬代尔）建立合作伙伴关系，在那里，本科生和研究生将有机会与公司代表会面，讨论他们的项目成果，参观公司的生产现场，从而了解他们工作的工业规模和商业意义。通过使用华盛顿州实验室开发的金属前体的草酸盐共沉淀，可以通过费托技术有针对性地设计用于长链烷烃生产的催化剂。这种制备技术在一个步骤中涉及所有金属组分，因此不需要传统的支撑材料。金属前体的相对量可以直接变化，以便调整用于通过CO氢化的选择性含氧化合物生产的组成。催化剂将由Co和Cu金属功能组成，具有Co核-Cu壳结构。 在组合化学瞬态动力学和密度泛函理论计算中提供的微动力学数据将包括在任何时刻的碳、氧和氢的“表面原子计数”，直到达到稳态条件。将执行在高表面覆盖率下在各种氧化物表面上的可吸收CoCu颗粒的能量分布，并将其与瞬态动力学数据相关联，以便优化高压CO加氢过程以生成长链含氧化合物。 预期这些研究工作将导致用于选择性C8-14含氧化合物生产的新一代催化剂。

Abstract Title: CO Hydrogenation to Long-chain Terminal Alcohols and Aldehydes: A Combined Approach by Transient Kinetics and Theoretical ModelingHomogeneous catalysts are widely used in industrial chemical processes for the production of long chain alcohols and aldehydes, which can then be used as feedstock for other chemical processes. This production process has several disadvantages as it involves several process steps and because the expensive precious noble metals in the catalysts have to be carefully recovered. An alternative way to produce long chain alcohols is by using a heterogeneous catalyst which adds hydrogen to carbon monoxide, employing catalysts made of earth abundant metals such as cobalt or iron. Such technology plays a major role in the petrochemical industry where the interest is in the production of long-chain hydrocarbons. There has been less application when it comes to the production of long chain oxygenated hydrocarbons. While it is known that different metals have different catalytic properties, the rational design of catalysts which can produce mostly useful products with minimum production of side-products remains a major challenge in industrial laboratories. However, recent research findings have shown that the heterogeneous catalysis route can in fact be a 'one-step, one-pot' process with no risk of valuable noble metal loss. This award, made to Professors Norbert Kruse and Jean-Sabin McEwen in the Center for Catalysis at Washington State University, aims at providing the essential scientific basis for the design of catalysts with superior catalytic activity and performance for the production of long-chain oxygenates from carbon monoxide. The implications of such a process are especially important in terms of closing the cost gap between chemical products that are traditionally based on fossil fuels and those which could be based on carbon monoxide instead. The PIs will also establish a partnership with the Phillips 66 Company Ferndale, WA refinery, where undergraduate and graduate students will be given the opportunity to meet with the company's representatives so as to discuss their project results, visit the company's production site and, consequently, understand industrial-scale and commercial implications of their work. The targeted design of catalysts for long-chain oxygenate production via the Fischer Tropsch technology becomes possible by using oxalate co-precipitation of metal precursors as developed in the laboratories Washington State. This preparation technique involves all metal components in a single step, so no classical support material is needed. Relative amounts of metal precursors can be straightforwardly varied so as to tune the composition for selective oxygenates production via CO hydrogenation. Catalysts will be comprised of Co and Cu metal functions, of the Co core-Cu shell structures. Microkinetic data as provided in combined chemical transient kinetics and density functional theory calculations will include a 'surface atom counting' of carbon, oxygen and hydrogen at any instant until steady state conditions are reached. Energy profiles for bimetallic CoCu particles on various oxide surfaces at high surface coverages will be performed and correlated to the transient kinetic data so as to optimize the high pressure CO hydrogenation process to long-chain oxygenates. It is anticipated that these research efforts will lead to a new generation of catalysts for selective C8-14 oxygenates production.