Efficient and Modular Methane Upgrading to Liquid Aromatics by Coupling Dehydroaromatization with Reactive Hydrogen Separation

拟议的研究项目旨在开发一种将甲烷转化为液体芳香族化合物的有效方法。甲烷向液态烃如芳烃的有效转化一直是石油工业中长期存在的问题，由于页岩气技术的最新进展和天然气原料的丰富而重新引起兴趣。通过催化脱氢芳构化（DHA）将甲烷直接转化为芳烃的提议与可以利用分布式原料的模块化制造技术兼容。然而，甲烷的转化率和经由DHA的芳族化合物的产率受到严格的限制。PI建议将联合收割机DHA与能够从烃类中反应性分离氢气的化学回路结合，以规避这种热力学限制并大幅提高芳烃产率。由于降低总转化率的固有热力学限制，DHA中甲烷的低转化率不能仅通过开发更好的催化剂来提高芳烃的选择性来解决。通过与氧化还原化学回路配对，可以实现氢（DHA的产物）的反应分离，这消除了热力学限制。该项目将联合收割机DHA与化学循环相结合，分为四个步骤：1）甲烷的DHA，2）从DHA流出物中选择性氧化氢气，3）除水，4）氢气再生。氢气的去除和再生将在单独的反应器中进行。首先将证明拟议循环中每个步骤的可行性，并优化操作条件和材料，以最大限度地提高每个步骤的效率。将构建一个实验室规模的半自动化装置，以评估在多个循环中采用所提出的策略的芳烃产率。本论文将设计、合成具有核-壳结构的固体氧化还原对，并对其在含芳烃原料中的选择性氢氧化反应进行评价。除了培训研究生外，该项目还包括将研究成果纳入化学工程课程和外联活动，旨在教育公众了解气候变化、可持续性和可再生能源技术的最新进展。将开发一个基于移动终端的软件平台，与目标学生群体建立联系，提供教育资源，促进与研究有关的职业选择，特别强调吸引和留住科学、技术、工程与数学（STEM）该奖项反映了NSF的法定使命，并通过使用基金会的智力价值进行评估，被认为值得支持和更广泛的影响审查标准。

The proposed research project aims to develop an efficient process for converting methane to liquid aromatic compounds. Efficient conversion of methane to liquid hydrocarbons, such as aromatics, has been a long-standing problem in the petroleum industry with renewed interest due to recent advances in shale gas technologies and the abundance of natural gas feedstocks. The proposed direct conversion of methane to aromatics via catalytic dehydroaromatization (DHA) is compatible with modular manufacturing technologies that can take advantage of distributed feedstocks. However, the conversion of methane and the yield of aromatic compounds via DHA are severely thermodynamically limited. The PI proposes to combine DHA with a chemical loop capable of reactively separating hydrogen from hydrocarbons to circumvent this thermodynamic limitation and substantially increase the aromatics yield.The low conversion of methane in DHA cannot be solely addressed by the development of better catalysts that improve selectivity to aromatics, due to the inherent thermodynamic limitations that lower the overall conversion. By pairing with a redox chemical loop, reactive separation of hydrogen (a product from DHA) can be achieved, which alleviates the thermodynamic limitation. The project will combine DHA with a chemical loop in four steps: 1) DHA of methane, 2) selective oxidation of hydrogen from the DHA effluent, 3) water removal, and 4) regeneration of hydrogen. The removal and regeneration of hydrogen will occur in separate reactors. The feasibility of each step in the proposed cycle will be demonstrated first and both the operating conditions and materials will be optimized to maximize the efficiency of each step. A laboratory-scale semi-automated setup will be constructed to evaluate the yield of aromatics with the proposed strategy in multiple cycles. Solid redox pairs with a core-shell structure will be designed, synthesized and evaluated for the selective hydrogen oxidation in aromatics-containing feeds. In addition to training graduate students, the project includes integration of research results into the chemical engineering curriculum and outreach activities aimed at educating the general public on climate change, sustainability and recent advances in renewable energy technologies. A mobile device based software platform will be developed to connect with targeted student groups, provide educational resources and promote research-related career options, with special emphasis on attracting and retaining students from underrepresented groups in science, technology, engineering and mathematics (STEM) programs.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.