NSF-BSF and Manufacturing USA: Lattice Oxygen Assisted Methane Activation for Modular Production of Fischer-Tropsch Ready Syngas

页岩气储量中的甲烷已成为一种重要的能源。甲烷在商业上用于通过重整和/或部分氧化生产氢气和液体燃料。尽管在催化剂的开发上已经投入了大量的努力，但传统的甲烷重整和部分氧化工艺受到各种固有的限制。这项拟议的研究旨在研究一种独特的甲烷部分氧化催化剂家族，这些催化剂具有健壮、活性和高效的特点。该项目将由北卡罗来纳州立大学研究小组和以色列内盖夫本古里安大学布莱克纳工业催化中心的一个小组(Moti Herskowitz博士和MIron Landau博士)共同实施。该项目团队旨在设计和表征一种既是活性甲烷部分氧化(POX)催化剂又是有效晶格氧(O2-)供体的核壳氧化还原催化剂。氧化还原催化剂由用于储存O2-的过渡金属氧化物核心、促进O2-/电子传导并抑制初级氧化物烧结/失活的离子-电子混合导电外壳和用于甲烷部分氧化的定制表面组成。催化剂在甲烷POX循环氧化还原模式下运行(步骤1)和用空气补充晶格氧(步骤2)。这项研究将研究(I)氧化还原催化剂中O2-的迁移途径和一些核壳材料之间的相容；(Ii)核-壳催化剂的控制合成和表征；(Iii)活性金属分散和反应机理研究。(4)模块填充床系统中甲烷痘的动力学建模和演示。建议的氧化还原催化剂是独一无二的，因为嵌入的O2-允许在没有蒸汽或氧气的情况下有效地氧化甲烷。活性O2-也能抑制结焦。钙钛矿壳提高了一次氧化物的耐烧结性。它还为活性金属分散和甲烷活化提供了理想的表面。初步研究表明，核壳式氧化还原催化剂具有优异的储氧能力(20W.T.%)、高的合成气选择性(96%)、活性(600℃下的高合成气产率)和结构稳定性(测试高达1100℃)。除了对研究生和本科生进行研究培训外，还计划通过外联活动，让代表人数不足的群体中的高中生参加STEM。该提议的项目是对美国制造业倡议的响应，并支持由美国化学工程师学会领导的美国能源部资助的快速制造研究所的使命。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Methane from shale gas deposits has become an important energy resource. Methane is commercially used to produce hydrogen and liquid fuels via reforming and/or partial oxidation. Although significant efforts have been devoted to catalyst development, conventional methane reforming and partial oxidation processes are subjected to various intrinsic limitations. The proposed research aims to investigate a unique family of catalysts for partial oxidation of methane that are robust, active, and highly efficient. The project will be carried out jointly by the North Carolina State University research group and a group from the Blechner Center for Industrial Catalysis at the Ben-Gurion University of the Negev in Israel (Drs. Moti Herskowitz and Miron Landau).The project team aims to design and characterize a class of core-shell redox catalysts that are both active methane partial oxidation (POx) catalysts and effective lattice oxygen (O2-) donors. The redox catalyst is composed of a transition metal oxide core for O2- storage, a mixed ionic-electronic conductive shell which facilitates O2-/electron conduction and inhibits primary oxide sintering/deactivation, and a tailored surface for methane partial oxidation. The catalyst is operated under a cyclic redox mode for methane POx (step 1) and lattice oxygen replenishment with air (step 2). The proposed research will investigate (i) O2- migration pathway in the redox catalyst and the phase compatibility between a number of core and shell materials; (ii) controlled synthesis and characterization of core-shell catalysts; (iii) active metal dispersion and reaction mechanism studies. (iv) kinetic modeling and demonstration of methane POx in a modular packed bed system. The proposed redox catalyst is unique since the embedded O2- allows effective methane oxidation without steam or oxygen. The active O2- also inhibits coke formation. The perovskite shell increases the sintering resistance of the primary oxide. It also provides an ideal surface for active metal dispersion and methane activation. Preliminary studies have led to core-shell redox catalysts with excellent oxygen storage capacity (20 w.t.%) and high syngas selectivity (96%), activity (high syngas yields at 600 degrees C) and structural stability (tested up to 1,100 degrees C). In addition to training graduate and undergraduate students in research there are plans to engage high school students from underrepresented groups in STEM through outreach activities. The proposed project is responsive to the Manufacturing USA initiative and supports the mission of the DOE-funded RAPID Manufacturing Institute led by the American Institute of Chemical Engineers.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.