|dc.description.abstract||The goal is of this project was to identify principles to guide the development of high performance dense film membranes for natural gas sweetening using hydrogen sulfide and carbon dioxide gas mixtures as models under aggressive sour gas feed conditions. To achieve this goal, three objectives were developed to guide this research.
The first objective was to study the performance of cellulose acetate (CA) and an advanced crosslinkable polyimide (PDMC) dense film membrane for H₂S separation from natural gas.
The second objective was to engineer those polymers to produce membrane materials with superior performance as measured by efficiency, productivity, and plasticization resistance, and the third objective was to determine the separation performance of these engineered membrane materials under more aggressive, realistic natural gas feeds, and to perform a detailed transport analysis of the factors that impact their performance.
Work on the first objective showed that in neat CA, penetrant transport is controlled by both the solubility and mobility selectivity, with the former being more dominant, leading to a high overall CO₂/CH₄ (33) and H₂S/CH₄ (35) ideal selectivities. However, in uncrosslinked PDMC, H₂S/CH₄ selectivity favored sorption only, whereas CO₂/CH₄ selectivity favored both mobility and sorption selectivity, leading to a high CO₂/CH₄ (37) but low H₂S/CH₄ (12) ideal selectivities. However, the latter polymer showed more plasticization resistance for CO₂.
In the second objective, both materials were engineered. A new technique referred to as “GCV-Modification” was introduced in which cellulose acetate was grafted using vinyltrimethoxysilane (VTMS), then hydrolyzed and condensed to form a polymer network. PDMC was also covalently crosslinked to enhance its performance. GCV-Modified CA showed significant performance improvements for H₂S and CO₂ removal; the permeability of CO₂ and H₂S were found to be 139 and 165 Barrer, respectively, which represented a 30X and 34X increase compared to the pristine CA polymer. The H₂S/CH₄ and CO₂/CH₄ ideal selectivities were found to be 39 and 33, respectively. Crosslinked PDMC showed a higher CO₂/CH₄ selectivity of 38 with a better plasticization resistance for CO₂ and H₂S.
In the third objective, these materials were tested under aggressive ternary mixtures of H₂S/CO₂/CH₄ with both vacuum and nonvacuum downstream. Even under aggressive feed conditions, GCV-Modified CA showed better performance vs. PDMC, and it remained were fairly stable, making it a potential candidate for aggressive sour gas separations, not only because of its significantly higher productivity, which will help decrease the surface area needed for separation, thereby reducing operating costs, but also because of the lower cost of the raw material GCV-Modified CA compared to PDMC.||