Natural Gas Sweetening by Ultra-Microporous Polyimides Membranes

Abstract

Most natural gas fields in Saudi Arabia contain around 10 mol.% carbon dioxide. The present technology to remove carbon dioxide is performed by chemical absorption, which has many drawbacks. Alternatively, membrane-based gas separation technology has attracted great interest in recent years due to: (i) simple modular design, (ii) potential cost effectiveness, (iii) ease of scale-up, and (iv) environmental friendliness. The state-of-the-art membrane materials for natural gas sweetening are glassy cellulose acetate and polyimide, which were introduced in the 1980s. In the near future, the kingdom is planning to boost its production of natural gas for power generation and increase the feedstock for new petrochemical plants. Therefore, the kingdom and worldwide market has an urgent need for better membrane materials to remove carbon dioxide from raw natural gas. The focus of this dissertation was to design new polyimide membrane materials for CO2/CH4 separation exhibiting high permeability and high selectivity relative to the standard commercial materials tested under realistic mixed-gas feed conditions. Furthermore, this study provided a fundamental understanding of structure/gas transport property relationships of triptycene-based PIM-polyimides. Optimally designed intrinsically microporous polyimide (PIM-PIs) membranes in this work exhibited drastically increased CO2/CH4 selectivities of up to ~75. In addition, a novel triptycene-based hydroxyl-containing polyimide (TDA1-APAF) showed 5-fold higher permeabilities over benchmark commercial materials such as cellulose acetate. Furthermore, this polyimide had a N2/CH4 selectivity of 2.3, thereby making it possible to simultaneously treat CO2- and N2-contaminated natural gas. Also, TDA1-APAF showed a CO2 permeability of 21 Barrer under binary 1:1 CO2/CH4 mixed-gas feed with a selectivity of 72 at a partial CO2 pressure of 10 bar which are significantly better than cellulose triacetate. These results suggest that TDA1-APAF polyimide is an excellent candidate membrane material for removal of CO2 and N2 from natural gas. Moreover, based on the collected data for CO2/CH4 mixed-gas experiments from this work and previously published reports, a new mixed-gas 2017 CO2/CH4 permeability/selectivity upper bound curve was initiated to reflect the actual performance including plasticization phenomena at high feed pressure and 10 bar CO2 partial pressure to simulate the real conditions of the wellhead pressure.