Membranes for olefin/paraffin separations
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The goal of this project was to develop a mixed matrix membrane with enhanced properties for propylene/propane separations. To start with the project, one of the high performance 6FDA based polyimides was identified as the polymer matrix for the rest of the project. The chosen polymer (6FDA-6FpDA) was successfully synthesized in the laboratory. During the synthesis process the key objectives for high molecular weight and low polydispersity index polymer were identified. High molecular weight 6FDA-6FpDA was achieved via laboratory synthesis and was tested successfully. After successful synthesis of the high performance polymer, pure polymer dense films were tested for transport properties. One problem identified with 6FDA-6FpDA polymer films for propylene/propane separations was plasticization. A major objective of this research was to develop a method for plasticization suppression. A carefully controlled annealing procedure with high temperature permeation experiments was used in this research to suppress plasticization in a mixed gas environment. To the best of our knowledge, this is for the first time plasticization suppression was achieved with pure polymeric membrane material for propylene/propane separations with pure and mixed gases. The observed mixed gas experimental selectivity was lower than the pure gas selectivity which was explained by the combination effect of dual mode and bulk flow effect. The last objective of this project was to successfully incorporate molecular sieve materials to form a mixed matrix membrane hybrid material with enhanced transport properties First, an ideal molecular sieve for propylene/propane separation was identified and characterized. AlPO-14 was chosen for this research following its success with propylene/propane pressure swing adsorption. Mixed matrix membranes were successfully produced and tested for enhanced transport properties. Both pure and mixed gas results showed promising results with enhanced propylene permeability and propylene/propane selectivity. The experimental results were modeled with the Cussler and Maxwell models. A modified Cussler model was presented in this work. This is the first time an enhancement in the transport properties with mixed matrix membrane for propylene/propane separations has been observed. This fundamental dense film work holds a bright future for the scale up of propylene/propane separations.