EFRI DChem: Next-generation Low Global Warming Refrigerants

EFRI DCHEM分布式化学制造项目名为EARTH（氢氟碳化合物环境应用研究），将在一个协调的框架内使用高保真实验、先进的计算机模拟和严格的分析方法来发现、合成和测试一种名为离子液体的新型液体，这种液体可用于分离、回收和将高全球变暖潜能值（GWP）的制冷剂混合物转化为安全产品。这项研究将由堪萨斯大学、圣母大学、德克萨斯农工大学和罗格斯大学的研究人员组成，由布鲁克海文国家实验室、橡树岭国家实验室和国家标准与技术研究所以及两个行业合作伙伴（Chemours和Iolitec）合作进行。鉴于必须从市场上清除大量高GWP制冷剂，该项目的技术、经济和环境影响是相当大的。回收制冷剂的市场价值超过10亿美元，防止高gwp制冷剂释放到地球大气中相当于减少1.75亿吨二氧化碳（或每年5000万辆汽车的排放量）。该项目有可能为制冷剂行业带来经济效益，并为美国100多家经EPA认证的回收商提供分布式化学品生产流程。该项目将采用多方面的战略，最大限度地与更广泛的科学界进行传播和知识共享。这四所大学致力于提供一个安全和包容的环境，并将招收5名博士生、1名博士后研究员和8名本科生。这些研究人员将接受科学和工程方面的跨学科培训，参加STEM研讨会和安全会议，并在合作大学、公司和国家实验室实习。该项目将提供回收和重新利用高gwp制冷剂所需的基础知识和创新。该项目建立在离子液体（ILs）的可调溶剂化特性的基础上，实现了与其他材料不可能分离的共沸HFC混合物。两个主要目标是：(1)设计具有高选择性和复杂系统容量的化学分离；(2)了解化学分离系统中发生的时间变化。六个基本目标将整合属性测量和状态方程建模（目标1），分子模拟和设计（目标2），先进材料开发（目标3），光谱学，散射和分子相互作用（目标4），过程建模和优化（目标5），以及实验室规模分离系统的设计和实施（目标6）。使用经过验证的实验方法，该团队将测量设计萃取蒸馏、吸收或膜工艺所需的热物理性质和汽液平衡。高通量分子动力学和蒙特卡罗模拟将用于计算溶解度（相平衡），选择性，以及大量制冷剂- il系统的输运性质，使用经过实验验证的分子力场。将合成含氟离子的新型il，探索连接制冷剂和il的“化学”空间。该团队将利用多种技术来确定制冷剂- il的相互作用，包括：以测量自扩散的脉冲梯度自旋回波（PG-SE）核磁共振实验、研究分子间相互作用的核Overhauser效应（NOE）实验、提供液体结构因子S(Q)的同步加速器x射线散射实验、径向对分布函数g(r)的傅里叶反正弦变换实验、动态比长尺度的准弹性中子散射（QENS）实验为例。在这项工作中设计的新型ILs的功效将通过设计优化和一组萃取蒸馏、吸收和膜分离过程的模拟和实验来证明。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

This EFRI DCHEM Distributed Chemical Manufacturing Project, named EARTH (Environmentally Applied Research Towards Hydrofluorocarbons), will use high-fidelity experiments, advanced computer simulations, and rigorous analytical methods in a coordinated framework to discover, synthesize, and test a new type of fluid called an ionic liquid that can be used to separate, recycle, and convert high global warming potential (GWP) refrigerant mixtures into safe products. The research will be conducted by a team of researchers located at the University of Kansas, the University of Notre Dame, Texas A&M University, and Rutgers University in collaboration Brookhaven National Lab, Oak Ridge National Lab and the National Institute of Standards and Technology and two industry partners (Chemours and Iolitec). The technical, economic, and environmental impacts of the project are considerable, given the large inventory of high GWP refrigerants that must be removed from the market. The market for recycling refrigerants is valued at more than a billion dollars and preventing the release of high-GWP refrigerants into the Earth’s atmosphere is equivalent to eliminating 175 million metric tons of CO2 (or annual emissions from 50 million cars). The project has the potential to economically benefit the refrigerants business and provide a distributed chemical manufacturing process for over 100 EPA certified recyclers in the U.S. A multi-faceted strategy will be employed to maximize dissemination and knowledge sharing with the broader scientific community. The four lead institutions are committed to providing a safe and inclusive environment and will recruit five PhD students, one post-doctoral researcher, and eight undergraduates. These researchers will be provided with cross-disciplinary training in science and engineering, attend STEM workshops and safety meetings, and intern in partnering universities, companies, and national labs.This project will provide the fundamental knowledge and innovation required to recycle and repurpose high-GWP refrigerants. The project is built upon the tunable solvation properties of ionic liquids (ILs) to realize the separation of azeotropic HFC mixtures that are not possible with other materials. The two primary goals are (1) designing chemical separations with high selectivity and capacity for complex systems and (2) understanding temporal changes that occur in chemical separation systems. Six fundamental aims will integrate property measurements and equation of state modeling (Aim 1), molecular simulations and design (Aim 2), advanced materials development (Aim 3), spectroscopy, scattering, and molecular interactions (Aim 4), process modeling and optimization (Aim 5), and design and implementation of lab-scale separation systems (Aim 6). Using proven experimental methods, the team will measure the thermophysical properties and vapor-liquid-equilibria required for designing an extractive distillation, absorption, or membrane process. High-throughput molecular dynamics and Monte Carlo simulations will be used to calculate the solubility (phase equilibrium), selectivity, and transport properties of a large number of refrigerant-IL systems using molecular force fields validated by experiment. New ILs with fluorinated ions will be synthesized to explore the “chemical” space connecting refrigerants and ILs. The team will utilize a number of techniques to determine refrigerant-IL interactions including: pulse-gradient-spin-echo (PG-SE) NMR experiments for measuring self-diffusion, nuclear Overhauser effect (NOE) experiments for studying intermolecular interactions, synchrotron X-ray scattering experiments for providing liquid structure factor S(Q), inverse Fourier sine transform for radial pair distribution function g(r), and quasi-elastic neutron scattering (QENS) for dynamical specific length scales as examples. The efficacy of the novel ILs designed in this work will be demonstrated via design optimization and a set of simulations and experiments for extractive distillation, absorption, and membrane separation processes.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.