Hydroxyl-Containing Aromatic Polyimides for Carbon Dioxide Removal from Natural Gas

Abstract

Natural gas is among the most dominant resources to provide energy supplies and Saudi Arabia ranks among the top 5 producers worldwide. However, prior to use of methane, natural gas has to be treated to remove other feed gas components, such as H2O, CO2, H2S, N2 and C2+ hydrocarbons. Most NG fields in KSA contain about 10 mol% carbon dioxide that has to be reduced to less than 2 mol% for pipeline delivery.

The conventional unit operations for natural gas separations, that is, molecular sieves, amine absorption, cryogenic distillation, and turbo expansion exhibit some disadvantages in terms of economics, operational flexibility or system footprint. One of the most attractive alternative is membrane technology in either standalone- or hybrid system configuration. Currently, the only two membrane materials used in industrial natural gas applications are cellulose acetate and polyimide, which have moderate permeability and fairly low selectivity when tested under realistic industrial conditions. The goal for future research is to develop unique polymeric membranes, which can at least partially replace conventional gas processing in future natural gas projects. This will support global economics and specifically the economy of Saudi Arabia. Newly developed polymeric materials must meet certain criteria to be used on a commercial scale. These criteria include: (i) high permeability and selectivity, (ii) processability into thin films, (iii) mechanical and thermal stability, and (iv) chemical stability against feed gas components.

This project focused on the removal of carbon dioxide from natural gas by developing and characterizing functionalized aromatic polyimide membrane materials that exhibit very high selectivity under aggressive mixed-gas conditions. 6FDA-DAR demonstrated a mixed-gas CO2/CH4 selectivity of 78 at a CO2 partial pressure of 10 bar with no pronounced indication of plasticization. Combining hydroxyl- and carboxyl groups in a miscible polyimide blend led to mixed-gas CO2/CH4 selectivity of 100 with no aging and no plasticization effects. This burgeoning membrane material has very high potential in large-scale natural gas separations with the best overall performance of any type developed to date.