SusChEM: Promotion of Nickel Catalysts for the Conversion of Biomass-derived Oils to Fuel-like Hydrocarbons

生物柴油由脂肪酸甲酯或所谓的FAME组成，是一种从植物油和动物脂肪中提取的燃料，近年来作为柴油的可再生替代品受到了极大的关注。然而，由于生物柴油含氧量高，储存稳定性较差，发动机兼容性问题，以及缺乏合适的原料，限制了生物柴油的广泛应用。该奖项授予肯塔基大学应用能源研究中心的Mark Crocker教授和Eduardo Santillan-Jimenez教授，旨在通过开发一种改进的工艺将植物油和动物脂肪转化为碳氢化合物来绕过这些缺点，这些碳氢化合物在化学上与石油衍生柴油难以区分，因此可以用作柴油的临时替代品。这一过程的一个主要特点是使用基于廉价、富含地球的镍的催化剂，而不是使用昂贵的贵金属催化剂。这项研究的另一个好处是，它将为学生提供生物燃料领域的实践经验，从而最终有助于满足可再生能源部门对高技能科学家和工程师日益增长的需求。该项目的第二个目标是建立针对肯塔基州当地学校的新的外展努力。具体地说，将开发一个“生物燃料游戏”，向K-12年级的学生传授有关石油燃料、生物燃料以及与其生产和使用相关的经济和环境成本的基本概念。该奖项的整个重点是与SusChEM的哲学相一致的。催化脱碳/脱碳(DeCOx)已被提议作为加氢处理的替代方案，用于脂肪和生物油的转化，以生产可再生的插入式碳氢燃料。事实上，脱碳不仅能源和氢气效率更高，而且比无害的金属催化剂更先进，而且不需要加氢处理中使用的硫化催化剂。研究人员已经证明，含有丰富的稀土和廉价的镍的特定催化剂的性能可以与通常用于催化脱碳的昂贵贵金属(钯和铂)相媲美。初步结果表明，添加少量铜或锡的镍催化剂可以提高该工艺的效率。然而，催化现象所起作用的基本原理还没有被彻底理解。这一项目的目的是更全面地了解这些促进作用，从而使该系统得到进一步改进。为此，将解决四个主要目标：1)通过微调催化活性相的活性来优化镍催化剂对燃料型碳氢化合物的选择性；2)通过对活性相进行电子和/或形态上的修饰来提高这些催化剂表现出的抗失活能力；3)建立基本的结构-活性关系以合理地解释这些变化对活性相的影响；以及4)通过机理和动力学研究来阐明具有代表性的原料-催化剂组合的反应机理和动力学参数。

Proposed Abstract Title:SusChEM: Development of Nickel Catalysts for the Conversion of Biomass-derived Oils to Fuel-like HydrocarbonsBiodiesel, which consists of fatty acid methyl esters or so-called FAMEs, is a fuel derived from vegetable oils and animal fats which has gained much attention in recent years as a renewable alternative to diesel fuel. However, a number of issues stemming from the high oxygen content of biodiesel,such as relatively poor storage stability and engine compatibility issues, have limited its widespread application, along with a lack of suitable feedstocks. This award, to Professors Mark Crocker and Eduardo Santillan-Jimenez at the University of Kentucky Center for Applied Energy Research, aims to circumvent these shortcomings by developing an improved process for the conversion of vegetable oils and animal fats to hydrocarbons which are chemically indistinguishable from petroleum-derived diesel, and hence, which can be used as a drop-in substitute for diesel. A key feature of this process is the use of a catalyst based on inexpensive, earth-abundant nickel, as opposed to the use of expensive precious metal catalysts. An added benefit of this research is that it will provide students with hands-on experience in the field of biofuels, thus ultimately helping to satisfy the growing demand for highly skilled scientists and engineers in the renewable energy sector. A second objective of this project is the establishment of new outreach efforts directed at local Kentucky schools. Specifically, a "biofuels game" will be developed, which teaches K-12 students basic concepts about petroleum fuels, biofuels, and the relative economic and environmental costs associated with their production and use. The entire focus of the award is aligned with the SusChEM philosophy.Catalytic decarboxylation/decarbonylation (deCOx) has been proposed as an alternative to hydrotreating for the conversion of lipids and bio-oils to produce renewable drop-in hydrocarbon fuels. Indeed, deCOx is not only more energy and hydrogen efficient, but it proceeds over benign metal catalysts, and does not require the sulfided catalysts used in hydrotreating. The investigators have shown that the performance of specific catalysts comprising earth-abundant and inexpensive Ni can rival that of the expensive precious metals (Pd and Pt) commonly used to catalyze deCOx. Preliminary results have shown that promotion of Ni catalysts with small amounts of Cu or Sn leads to enhancements in the efficiency of the process. However, the underlying principles of the catalytic phenomena at play are not thoroughly understood. This project aims at a more complete understanding of these promotion effects, which in turn should allow further improvements to the system. To this end, four main objectives will be addressed: 1) the selectivity of Ni catalysts towards fuel-like hydrocarbons will be optimized by fine-tuning the activity of the catalytically active phase; 2) the resistance to deactivation shown by these catalysts will be improved by modifying the active phase electronically and/or morphologically; 3) fundamental structure-activity relationships will be established to rationalize the effect of these changes on the active phase; and 4) mechanistic and kinetic studies will be employed to elucidate the reaction mechanism and kinetic parameters for representative feed-catalyst combinations.