Collaborative Research: Reverse-Selective Membrane Materials for the Purification of Hydrogen and Other Light Gases

摘要提案标题：用于净化氢气和其他轻气体的反选择性膜材料提案编号：CTS-0515425首席研究员：Benny Freeman机构：德克萨斯大学奥斯汀分校该合作提案的目标是制定和优化新一代气体分离膜材料，该材料设计用于选择性渗透较大的极性或四极物质，而不是较小的非极性物质。 在这项工作中的膜材料是橡胶状的，交联的共聚物网络，专门配制，以实现较高的溶解度选择性较大的极性或四极气体分子比较小的非极性分子，同时最大限度地减少尺寸筛分。该网络是通过聚乙二醇（PEG）丰富的丙烯酸酯和二丙烯酸酯单体的共聚反应制备的。对非优化膜的初步渗透研究表明，可以用基于PEG的网络实现二氧化碳相对于氢气的优先传输，对于非促进传输膜，二氧化碳渗透性和选择性的组合最高。这些中试研究还表明，气体分离性能对网络结构的细节敏感，交联密度和主链侧基的变化导致渗透性和总体选择性的显著变化。 为了充分实现这类新的膜的潜力，提出了一个系统的实验研究的基础上的网络与控制的结构和交联密度的变化的制备和表征。膜将被战略性地设计以优化其在分离性能和整体机械完整性方面的性能。理解网络结构和气体分离性能之间关系的关键是聚合物链动力学和局部自由体积，与膜的扩散选择性有关。该项目将导致加强基本的理解，以链动力学和形态与橡胶网络的气体分离性能的相关性，以及这种工业相关的膜材料类的分子设计范例的出现。除了与该提案相关的基本材料和膜科学目标外，更广泛的影响还包括这些新膜作为工业气体分离过程替代品的潜在应用，这些工业气体分离过程基于繁琐的能源密集型方法，如吸收。 这项工作将通过研究生培训产生重要的教育效益。 此外，计划与液化空气集团的工业联系以及与CSIRO（澳大利亚）的互动将为气体分离膜的工业目标和优先事项提供直接投入，并为这些材料的表征提供更多资源。 这项工作可能导致一类新的膜，用于工业上重要的气体分离。

AbstractProposal Title: Reverse-selective Membrane Materials for the Purification of Hydrogen and Other Light GasesProposal Number: CTS-0515425Principal Investigator: Benny FreemanInstitution: University of Texas at AustinThe objective of this collaborative proposal is the formulation and optimization of a new generation of gas separation membrane materials designed for the selective permeation of larger, polar or quadrupolar species over smaller, non-polar species. The membrane materials in this work are rubbery, crosslinked copolymer networks specifically formulated to achieve high solubility selectivity for larger, polar or quadrupolar gas molecules over smaller, non-polar molecules while simultaneously minimizing size sieving. The networks are prepared via copolymerization of polyethylene glycol (PEG)-rich acrylate and diacrylate monomers. Preliminary permeation studies on non-optimized membranes have demonstrated that preferential transport of carbon dioxide over hydrogen can be accomplished with PEG-based networks, with the highest combination of carbon dioxide permeability and selectivity yet reported for non-facilitated transport membranes. These pilot studies also indicate that the gas separation performance is sensitive to the details of the network structure, with variations in crosslink density and backbone pendant groups leading to significant changes in both permeability and overall selectivity. To fully realize the potential of this new class of membranes, a systematic experimental study is proposed based on the preparation and characterization of networks with controlled variations in structure and crosslink density. The membranes will be strategically designed to optimize their performance both in terms of separation properties and overall mechanical integrity. Keys to understanding the relationship between network structure and gas separation properties are the polymer chain dynamics and local free volume, as related to the diffusivity selectivity of the membranes. The project will lead to enhanced fundamental understanding as to the correlation of chain dynamics and morphology with gas separation performance for rubbery networks, and the emergence of molecular-based design paradigms for this industrially-relevant class of membrane materials. In addition to the fundamental materials and membrane science goals associated with the proposal, broader impacts include the potential application of these new membranes as replacements for industrial gas separation processes based on cumbersome, energy-intensive methods such as absorption. This work will lead to important educational benefits through graduate student training. Further, the planned industrial liaison with Air Liquide and interaction with CSIRO (Australia) will provide direct input regarding industrial goals and priorities for gas separation membranes, and expanded resources for the characterization of these materials. This work could lead to a new class of membranes for industrially important gas separations.