Collaborative Research: Development and Application of a Molecular and Process Design Framework for the Separation of Hydrofluorocarbon Mixtures

合作研究：氢氟碳化合物混合物分离的分子和工艺设计框架的开发和应用

• 批准号: 1917480
• 负责人: Mark Shiflett
• 金额: $ 29.97万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1917480&HistoricalAwards=false
• 关键词: Collaborative; Research; Development; Application; Molecular

Refrigerators and heat pumps use a substance called a refrigerant to move heat between two spaces. Prior to the late 1980s, refrigerants often contained chlorfluorocarbons, but these materials were phased out because of their high ozone depletion potential. Mixtures of hydrofluorocarbons appeared on the market as replacement refrigerants. Hydrofluorocarbons (HFC) do not deplete the Earth's ozone layer, but they to do tend to trap greenhouse gases in the atmosphere, measured as global warming potential, prompting a concerted effort to phase out the use of high global warming potential HFCs. The phase out of these materials is complicated by the fact that there are thousands of tons of refrigerant mixtures that contain both low and high global warming potential compounds, and there is no viable method for separating and reclaiming the components. The separation of low and high global warming HFCs is complex because they are azeotropic or near-azeotropic materials, meaning they are chemically similar and behave like a single (pure) fluid. The goal of the project is to develop tools and processes that enable the separation of high and low global warming potential HFCs, allowing the recovery and reuse of the low global warming potential HFCs. To accomplish this goal, an integrated molecular and chemical process design framework will be developed to engineer novel ionic liquid-based HFC separation technologies. The approach will unify "top-down" computer-aided molecular design with "bottom-up" experimentally-driven approaches to more efficiently identify new separation agents for HFC azeotropic mixtures. The engineering framework will be widely applicable to other chemical separation processes, including that of next-generation refrigerants such as hydrofluoro-olefins and hydrochlorofluoro-olefins. The physical property data and computational tools will be disseminated through national data repositories and open source agreements, respectively. The project also provides experiential training opportunities for two graduate students who will interface with industrial partners. It is hypothesized that ionic liquids can be designed to achieve unprecedented separation efficiency for azeotropic HFC mixtures. However, there are millions of potential ionic liquids, making a trial-and-error search infeasible. The overall goals of this project are: i) to establish a unified framework for ionic liquid molecular design and separation process configuration optimization and ii) to engineer new technologies to enable recycling of HFC refrigerants. The collaborative project integrates state-of-the-art methods in pure and mixed gas solubility measurements, high throughput molecular simulations, and superstructure optimization into a single, unified framework. Both experimental physical property measurements and laboratory-scale demonstrations will be used to validate the multiscale computational models. The proposed framework offers a systematic approach to rapidly engineer ionic liquid solvent and separation processes. The framework is general purpose and has the potential to enable dramatically faster discovery of novel separation solvents and systems well beyond the HFC domain.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.

Refrigerators and heat pumps use a substance called a refrigerant to move heat between two spaces. Prior to the late 1980s, refrigerants often contained chlorfluorocarbons, but these materials were phased out because of their high ozone depletion potential. Mixtures of hydrofluorocarbons appeared on the market as replacement refrigerants. Hydrofluorocarbons (HFC) do not deplete the Earth's ozone layer, but they to do tend to trap greenhouse gases in the atmosphere, measured as global warming potential, prompting a concerted effort to phase out the use of high global warming potential HFCs. The phase out of these materials is complicated by the fact that there are thousands of tons of refrigerant mixtures that contain both low and high global warming potential compounds, and there is no viable method for separating and reclaiming the components. The separation of low and high global warming HFCs is complex because they are azeotropic or near-azeotropic materials, meaning they are chemically similar and behave like a single (pure) fluid. The goal of the project is to develop tools and processes that enable the separation of high and low global warming potential HFCs, allowing the recovery and reuse of the low global warming potential HFCs. To accomplish this goal, an integrated molecular and chemical process design framework will be developed to engineer novel ionic liquid-based HFC separation technologies. The approach will unify "top-down" computer-aided molecular design with "bottom-up" experimentally-driven approaches to more efficiently identify new separation agents for HFC azeotropic mixtures. The engineering framework will be widely applicable to other chemical separation processes, including that of next-generation refrigerants such as hydrofluoro-olefins and hydrochlorofluoro-olefins. The physical property data and computational tools will be disseminated through national data repositories and open source agreements, respectively. The project also provides experiential training opportunities for two graduate students who will interface with industrial partners. It is hypothesized that ionic liquids can be designed to achieve unprecedented separation efficiency for azeotropic HFC mixtures. However, there are millions of potential ionic liquids, making a trial-and-error search infeasible. The overall goals of this project are: i) to establish a unified framework for ionic liquid molecular design and separation process configuration optimization and ii) to engineer new technologies to enable recycling of HFC refrigerants. The collaborative project integrates state-of-the-art methods in pure and mixed gas solubility measurements, high throughput molecular simulations, and superstructure optimization into a single, unified framework. Both experimental physical property measurements and laboratory-scale demonstrations will be used to validate the multiscale computational models. The proposed framework offers a systematic approach to rapidly engineer ionic liquid solvent and separation processes. The framework is general purpose and has the potential to enable dramatically faster discovery of novel separation solvents and systems well beyond the HFC domain.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.

项目成果

Phase Equilibria and Diffusivities of HFC-32 and HFC-125 in Ionic Liquids for the Separation of R-410A

用于分离 R-410A 的离子液体中 HFC-32 和 HFC-125 的相平衡和扩散率

• DOI: 10.1021/acssuschemeng.1c06252
• 发表时间: 2022
• 期刊: ACS Sustainable Chemistry & Engineering
• 影响因子: 8.4
• 作者: Baca, Kalin R.;Olsen, Greta M.;Matamoros Valenciano, Lucia;Bennett, Madelyn G.;Haggard, Dorothy M.;Befort, Bridgette J.;Garciadiego, Alejandro;Dowling, Alexander W.;Maginn, Edward J.;Shiflett, Mark B.
• 通讯作者: Shiflett, Mark B.

First Measurements for the Simultaneous Sorption of Difluoromethane and Pentafluoroethane Mixtures in Ionic liquids Using the Integral Mass Balance Method

使用积分质量平衡法首次测量离子液体中二氟甲烷和五氟乙烷混合物的同时吸附

• DOI: 10.1021/acs.iecr.2c00497
• 发表时间: 2022
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: Baca, Kalin R.;Broom, Darren P.;Roper, Mark G.;Benham, Michael J.;Shiflett, Mark B.
• 通讯作者: Shiflett, Mark B.

Phase Equilibria, Diffusivities, and Equation of State Modeling of HFC-32 and HFC-125 in Imidazolium-Based Ionic Liquids for the Separation of R-410A

• DOI: 10.1021/acs.iecr.0c02820
• 发表时间: 2020-09
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: A. Morais;Abby N. Harders;Kalin R. Baca;Greta M. Olsen;Bridgette J. Befort;A. Dowling;E. Maginn;M. Shiflett

Multicomponent Refrigerant Separation Using Extractive Distillation with Ionic Liquids

• DOI: 10.1021/acs.iecr.2c00937
• 发表时间: 2022-06
• 期刊: Industrial & Engineering Chemistry Research
• 作者: Ethan A. Finberg;Tessie L. May;M. Shiflett

Process Designs for Separating R-410A, R-404A, and R-407C Using Extractive Distillation and Ionic Liquid Entrainers

• DOI: 10.1021/acs.iecr.1c02891
• 发表时间: 2021-10
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: Ethan A. Finberg;M. Shiflett