EAGER: Selectivity Control in Direct Non-oxidative Methane Conversion over Fe?SiO2 Catalyst by Manipulating the Feed Composition

EAGER：通过控制进料组成来控制 Fe?SiO2 催化剂上直接非氧化甲烷转化的选择性

• 批准号: 1642405
• 负责人: Dongxia Liu
• 金额: $ 10万
• 依托单位: University of Maryland, College Park
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-07-15 至 2019-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1642405&HistoricalAwards=false
• 关键词: EAGER; Selectivity; Control; Direct; Non

The project is an exploratory study aimed at confirming and extending a report published in Science (Guo et al. 2014) of an iron-silica catalyst and reaction conditions leading to direct, non-oxidative, methane conversion (DNMC) to higher-value chemical feedstocks including ethylene, benzene, and naphthalene. The technology, if proven, represents a significant technological breakthrough with transformative potential for converting the large quantities of shale gas derived methane to transportable, high-value chemical feedstocks rather than the current practice of flaring with associated emissions of the greenhouse gas, carbon dioxide.The underlying challenge in methane chemistry is active and selective catalytic conversion to form fuels and chemicals in an economical approach without deactivating the catalyst via thermal processes or coke formation. The PIs will elucidate the reaction pathways and mechanisms in the DNMC reactions over Fe©SiO2 catalyst by ex-situ analysis of catalyst fine structures and using Molecular Beam Mass Spectroscopy (MBMS)to analyze both stable and radical gas phase reaction intermediates and products. The study will also evaluate the effects of hydrogen and hydrocarbon species on catalysis as a parameter to control DNMC and demonstrate its applicability in context of the following specific aims: (i) Successfully synthesize the catalyst and understand its activation mechanism; (ii) Systematically tune the product selectivity and methane conversion by controlling the feed stream compositions; (iii) Rigorously describe the kinetic effects of feed composition on methane reaction pathways and catalyst deactivation. The proposed research will provide specific guidance for the development of catalysts and processes useful in manufacturing value-added products from low cost methane gas resources. To this end the broader impact of a practical DNMC process would transform the fuels and chemicals industry while reducing the atmospheric burden of CO2 and the impact of fossil resources on global warming. The technology could also have potential application in other areas such as processing of pyrolysis gases from biorenewable sources. The study will create a unique opportunity for graduate and undergraduate students to experience cross-cutting education in aspects of catalysis, reaction engineering, gas analysis, and chemical kinetics.This award is co-funded by the Engineering Directorate Office of Emerging Frontiers and Multidisciplinary Activities.

该项目是一项探索性研究，旨在证实和扩展发表在《科学》杂志上的一篇报告(Guo等人。2014)的铁-二氧化硅催化剂，以及导致甲烷直接、非氧化转化(DNMC)为更高价值的化工原料(包括乙烯、苯和萘)的反应条件。如果得到证实，这项技术代表着一项具有变革潜力的重大技术突破，可以将大量页岩气衍生的甲烷转化为可运输的高价值化学原料，而不是目前伴随温室气体二氧化碳排放而燃烧的做法。甲烷化学的潜在挑战是活性和选择性催化转化，以一种经济的方法形成燃料和化学品，而不会通过热过程或焦炭形成使催化剂失活。PIS将通过对催化剂精细结构的非原位分析，以及使用分子束质谱仪(MBMS)分析稳定和自由基气相反应中间体和产物，阐明在Fe-SiO_2催化剂上DNMC反应的反应途径和机理。这项研究还将评估氢和碳氢化合物物种对催化的影响，并将其作为控制DNMC的参数，并展示其在以下特定目标下的适用性：(I)成功合成催化剂并了解其活化机理；(Ii)通过控制进料组成系统地调节产物选择性和甲烷转化率；(Iii)严格描述进料组成对甲烷反应路径和催化剂失活的动力学影响。拟议的研究将为开发可用于利用低成本甲烷气体资源生产附加值产品的催化剂和工艺提供具体指导。为此，实际的DNMC进程的更广泛影响将改变燃料和化学品行业，同时减少二氧化碳的大气负担和化石资源对全球变暖的影响。该技术还可能在其他领域有潜在的应用，如来自生物可再生能源的热解气体的处理。这项研究将为研究生和本科生创造一个独特的机会，在催化、反应工程、气体分析和化学动力学方面体验交叉教育。该奖项由新兴前沿和多学科活动工程局办公室共同资助。

项目成果

Direct Non‐Oxidative Methane Conversion in a Millisecond Catalytic Wall Reactor

毫秒催化壁反应器中的直接非氧化甲烷转化

• DOI: 10.1002/ange.201903000
• 发表时间: 2019
• 期刊: Angewandte Chemie
• 作者: Oh, Su Cheun;Schulman, Emily;Zhang, Junyan;Fan, Jiufeng;Pan, Ying;Meng, Jianqiang;Liu, Dongxia
• 通讯作者: Liu, Dongxia

Mesopore differences between pillared lamellar MFI and MWW zeolites probed by atomic layer deposition of titania and consequences on photocatalysis

• DOI: 10.1016/j.micromeso.2018.10.009
• 发表时间: 2019-03
• 期刊: Microporous and Mesoporous Materials
• 影响因子: 5.2
• 作者: Junyan Zhang;Zheng Lu;Wei Wu;Dat T. Tran;Wenjin Shang;Huiyong Chen;Y. Lei;Zhenglong Li;Mei Wang;T. Woehl;Dongxia Liu

Synthesis of hierarchical lamellar MFI zeolites with sequential intergrowth influenced by synthetic gel composition

• DOI: 10.1016/j.micromeso.2018.08.007
• 发表时间: 2019-02
• 期刊: Microporous and Mesoporous Materials
• 影响因子: 5.2
• 作者: L. Emdadi;Dat T. Tran;Emily Schulman;Lu Wei;Wenjin Shang;Huiyong Chen;Dongxia Liu

Three-step cascade over a single catalyst: synthesis of 5-(ethoxymethyl)furfural from glucose over a hierarchical lamellar multi-functional zeolite catalyst

• DOI: 10.1039/c8ta01242c
• 发表时间: 2018-05-07
• 期刊: JOURNAL OF MATERIALS CHEMISTRY A
• 影响因子: 11.9
• 作者: Bai, Yuanyuan;Wei, Lu;Liu, Dongxia
• 通讯作者: Liu, Dongxia