To date there exists a great deal of energetic and economic inefficiency in the separation of olefins from paraffins because the principal means of achieving industrial purity requirements is accomplished with very energy intensive cryogenic distillation. Mitigation of the severe energy intensity of the propylene/propane separation has been identified as one of seven chemical separations which can change the landscape of global energy use, and membranes have been targeted as an emerging technology because they offer scalability and lower capital and operating costs. The focus of this work was to evaluate a new direction of material development for the very industrially relevant propylene/propane separation using membranes. The objective was to develop a rational design approach for generating highly selective membranes using a relatively new platform of materials known as polyimides of intrinsic microporosity (PIM-PIs), the prospects of which have never been examined for the propylene/propane separation. Structurally, PIMs comprise relatively inflexible macromolecular architectures integrating contortion sites that help disrupt packing and trap microporous free volume elements (< 20 Å). To date most of the work reported in the literature on this separation is based on conventional low free volume 6FDA-based polyimides which in the best case show moderate C3H6/C3H8 selectivities (<20) with C3H6 permeabilities too low to garner industrial interest. Due to propylene and propane’s relatively large molecular size, we hypothesized that the use of more open structures can provide greater accessibility to the pores necessary to enhance membrane sieving and flux. It has been shown for numerous key gas separations that introduction of microporosity into a polymer structure can defy the notorious permeability/selectivity tradeoff curve and induce simultaneous boosts in both permeability and selectivity. The cornerstone approach to designing state of the art high performance PIM-PI membranes for the light gas separations involving maximizing the intra-segmental rigidity of the polymer chain was applied to the C3H6/C3H8 separation. A study regarding a stepwise maximization of intra-molecular rigidity and its effects on C3H6/C3H8 permeation was evaluated by conducting systematic structural modifications to high performance PIM-PIs. State of the art increases in performance were observed in pure-gas measurements as there were significant increases in C3H6/C3H8 selectivity and C3H6 permeability upon doing so. However, mixed-gas measurements showed that there were 65% losses in selectivity due to competitive sorption and mainly plasticization. Based on the conclusions drawn, a fundamental departure from conventional PIM design principles was used, instead emphasizing enhancing inter-chain interactions by introduction of a flexible diamine and functionalization with hydroxyl groups to attempt to immobilize the polymer chains. In doing so, the polymer chains may be able to pack more efficiently and upon sub-Tg annealing cause a microstructural reorganization to form a coplanarized configuration due to the combination of inter-chain charge transfer complexes (CTC) and hydrogen bonding networks. This approach successfully mitigated plasticization, but more importantly resulted in a tightening of the microstructure, especially in the ultra-microporous range (<7 Å) thereby yielding significant boosts in C3H6/C3H8 selectivity. Based on the PIM platform and novel polymer design approach thereof, the C3H6/C3H8 upper bound was thrust to new limits and led to the generation of the most selective solution processable polymers reported for the C3H6/C3H8 separation. Although the PIM platform has redefined the polymer upper bound, the permeability/selectivity tradeoff still endures, as the C3H6 permeabilities were on the order of 1 to 3.5 Barrer for the most selective polymers. To bridge that gap in permeability, several different approaches were taken. For the first time attempted for C3H6/C3H8 separation, high temperature heating of a PIM-PI to form thermally-rearranged and carbon molecular sieve membranes was employed. The TR membrane showed increased C3H6 permeability and about 50% losses in C3H6/C3H8 selectivity, while the CMS membrane formed at 600 oC showed modest gains in C3H6/C3H8 selectivity with significant improvements in C3H6 permeability. Finally, hybrid nanocomposite membranes incorporating a metal-organic framework structure into a PIM-PI matrix was used. ZIF-8, which has demonstrated high diffusive selectivities for C3H6/C3H8, was dispersed within the polymer, since previous work by the Koros group indicated that its incorporation into polyimide matrices can facilitate major improvements in both C3H6/C3H8 selectivity and C3H6 permeability compared to the respective neat polymer. Focus was directed towards attempting to improve polymer/nanoparticle adhesion by enhancing the interactions between the polymer and filler particles to mitigate the interfacial defects notorious in mixed-matrix membranes (MMM). To do so, ZIF-8 was dispersed into one of the best performing hydroxyl functionalized PIM-PI for the C3H6/C3H8 separation. The highest loaded mixed-matrix membrane in a glassy polymer to date of 65% (w/w) was achieved. The membranes showed pure-gas selectivities ranging from 34 with 10 Barrer at 30% loading to 43 with 38 Barrer at 65% loading. Strong performance and plasticization resistance were sustained in mixed-gas experiments even to feed pressures approaching the vapor pressure of the C3H6/C3H8 mixture, as selectivities well over 20 were achieved with high permeabilities, thereby demonstrating the potential commercial viability. Based on the work reported in this dissertation, we hope to help lay a framework to be able to tailor membrane performance and future membrane design to meet the demands of the different applications of the propylene/propane separation and hence show that there can be a marketplace for membranes in the separation. These include the debottlenecking of cryogenic distillation towers for production of polymer-grade propylene (99.5%) to reduce the associated extensive energy load, production of chemical-grade propylene (92-95% propylene), or for the recovery and recycling of olefins from reactor purges of petrochemical processes.
|Date made available
|KAUST Research Repository