The research aimed to develop chemically modified PIM-1s for use in adsorption and gas separation processes. In particular, the nitrile group in PIM-1 was converted to several different functional groups to manipulate the interaction ability of PIM-1 with different species. Synthesis of PIM-1 was achieved by two different methods, using both the low (72h, 65 °C) and the high temperature (40 min, 160 °C) methods. Hydrolysis of PIM-1 was performed in the presence of 20% and 10% NaOH solutions (1:1 H2O/ethanol) at 120 and 100 °C, respectively. The reaction resulted in a mixture of hydrolysis products. The composition of the polymer has a profound effect on the final performance of the polymer. Powder samples of hydrolysed PIMs were used in the research. The reduction of nitrile to primary amine was achieved using borane dimethyl sulphide complex, resulting in amine PIM-1. Both membrane and powder forms of amine PIMs were studied. The reaction of PIM-1 with ethanolamine and diethanolamine produced hydroxyalkylaminoalkylamide PIMs. The combination of all available techniques (ATR-IR, solution and solid state NMR, TGA, Elemental analysis, UV, GPC, MALDI-ToF, low pressure N2 sorption) was used to characterise the polymers. Gas sorption studies of modified PIMs showed that the sorption capacities of polymer altered depend on the modification. Hydrolysed PIMs showed reduced CO2 uptake. Ethanolamine modified PIM showed reduced CO2 uptake along with even more reduced N2 uptake, leading to enhanced CO2/N2 ideal selectivity at 1 bar. Amine modification increased the CO2 uptake of the polymer, while showing the same N2 uptake. Enhanced sorption selectivity was also achieved by amine PIM-1. Although chemical modifications reduced the permeability of the membranes, enhanced gas selectivity was obtained. Enhanced H2/CO2 selectivity placed amine PIM-1 above the 2008 Robeson upper bound. The relationship between the degree of conversion and permeability of amine PIM-1 was studied in detail. The effect of temperature and pressure on the permeability of amine PIM was studied, using several different temperatures and pressures. Ethanolamine modified PIM showed size selective behaviour by enhanced H2/N2 and H2/CH4 selectivities, and it crossed the 2008 Robeson upper bounds. Dye adsorption studies revealed that chemical modification manipulated the interaction ability of PIM-1. PIM-1 showed high affinity for neutral dye. While hydrolysed PIMs showed high affinity for cationic species, amine and ethanolamine modified PIMs displayed high affinity for anionic dyes. The factors affecting the uptake capacity of PIM-1, including temperature and pH, were studied along with kinetics of dye adsorption. Thermal treatments of modified PIMs and their structural characterisation were performed. The adsorption and separation performances of thermally treated and untreated modified PIMs were compared.

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.

This research aimed to develop new polymeric materials for use in membrane or adsorption processes for carbon dioxide capture. In particular, it explored the synthesis, characterization and properties of polymers incorporating a spiro-center. A dianhydride containing a spiro-center (An-1), suitable for use in the preparation of polyimides, was synthesized using a previously reported procedure. The spiro-center makes the structure of the resulting polymers (PIM-PIs) similar to polymers of intrinsic microporosity (PIMs), which are known for their high internal surface area and outstanding membrane permeation properties. PIM-polyimides PIM-PI-1 and PIM-PI-5 were successfully synthesized and characterized, and membranes prepared for permeation studies. For PIM-PI-5, gas permeation data were obtained for the first time and were shown to be in reasonable agreement with values predicted by a group contribution method. To produce membranes with even better gas permeation properties, hydroxyl-containing PIM-polyimides were introduced. The presence of a hydroxyl group in the ortho position of the imide linkage made it possible to thermally rearrange the PIM-polyimide to a PIM-polybenzoxazole (PIM-PBO) at 450 oC in an inert atmosphere. PIM-PI-OH-1 with high enough molecular weight to form a freestanding membrane was successfully synthesized using two different synthetic methods: thermal imidization and one-step polycondensation. The PIM-PI-OH-1 polymers prepared by both synthetic methods were compared in terms of gas permeation properties and CO2 uptake capacity, before and after thermal rearrangement. As expected, for polymers prepared by both methods, a significant enhancement was observed in the membranes gas permeation properties upon thermal rearrangement. Ethanol treatment was also performed on the thermally rearranged polymers, which resulted in a large increase in their permeability. The effect of aging was investigated on the ethanol treated PIM-PBO-1 membranes. It was observed that the membranes gradually lose the extra permeability created upon ethanol treatment and return to close to their original permeability value. To increase the concentration of thermally rearrangeable sites in the polymers, a dianhydride (An-2) with a smaller structure and lower molecular weight comparing to the An-1 was synthesized. A copolymer (copolymer-OH(1-2)), was synthesized using An-1 and An-2 (1:1). Gas permeation measurements were performed on the thermally rearranged polymer before and after ethanol treatment. A slight enhancement in the polymer’s selectivity toward CO2/N2 and CO2/CH4 gas pairs was observed, while maintaining the permeability. Having the same aim, PIM-PI-OH-3 was prepared using a smaller and a more rigid diamine, compared to the diamine used in the preparation of PIM-PI-OH-1. Gas permeation studies of the thermally rearranged membrane before and after ethanol treatment showed a significant increase in O2/N2 selectivity, which passed the Robeson 2008 upper bound. In adsorption experiments, CO2 uptake was higher than for PIM-PI-OH-1 and its thermally rearranged product.

This dissertation addresses the rational design of intrinsically microporous solutionprocessable polyimides and ladder polymers for highly permeable and highly selective gas transport in cornerstone applications of membrane-based gas separation – that is, air enrichment, hydrogen recovery and natural gas sweetening. By virtue of rigid and contorted chains that pack inefficiently in the solid state, polymers of intrinsic microporosity (PIMs) have the potential to unite the solution-processability, mechanical flexibility and organic tunability of commercially relevant polymers with the microporosity characteristics of porous crystalline materials. The performance enhancements of PIMs over conventional low-free-volume polymers have been primarily permeability-driven, compromising the selectivity essential to commercial viability. An approach to unite high permeability with high selectivity for performance transcending the state-of-the-art in air and hydrogen separations was demonstrated via a fused-ring integration of a three-dimensional, shape persistent triptycene moiety optimally substituted with short, branched isopropyl chains at the 9,10-bridgeheads into a highly inflexible backbone. The resulting polymers exhibited selectivities (i.e., O2/N2, H2/N2, H2/CH4) similar to or higher than commercial materials matched with permeabilities up to three hundred times higher. However, the intra-chain rigidity central to such conventional PIM-design principles was not a singular solution to suppression of CO2-induced plasticization in CO2/CH4 mixedgas separations. Plasticization diminishes the sieving capacity of the membrane, resulting in costly hydrocarbon losses that have significantly limited the commercialization of new polymers. Unexpectedly, the most permeable and selective PIMs designed for air and hydrogen separations strongly plasticized in 50:50 CO2/CH4 mixtures, enduring up to three-fold increases in mixed-gas CH4 permeability by 30 bar and strong drops in selectivity. Instead, a paradigm shift emphasizing inter-chain rigidity was demonstrated for the PIM-type polyimides via introduction of a flexible diamine functionalized with hydroxyl groups. Intra-chain flexibility may permit short-range coplanarization of backbone segments which facilitates inter-chain interactions likely comprising charge transfer complexes over the N-phenyl imide bond and hydrogen bonding. Relative to commercial cellulose acetate membranes at a representative 10 bar CO2 partial pressure, the resulting polyimide exhibited two-fold increases in mixed-gas CO2/CH4 selectivity (~50) concurrent with nearly 10-fold higher CO2 gas permeability. Similar design principles were drawn for ladder polymers.

Control at the molecular level over porous solid-state materials is of prime importance for fine-tuning the local structures, as well as the resultant properties. Traditional porous solid-state materials such as zeolite and activated carbon are the benchmarks in the current market with vital applications in sorption and heterogeneous catalysis. However, the adjustments of pore size and geometry of those materials, which are essential for the broader aspect of modern prominent applications, remain challenging. Reticular chemistry has emerged as a dominant tool toward the ‘designed syntheses’ of porous crystalline frameworks (e.g. metal-organic frameworks (MOFs)) with a specific pore system. This dissertation illustrates the power of reticular chemistry and its use in the directional assembly of highly coordinated MOF materials, as well as their potential applications such as gas storage, natural gas upgrading, and light hydrocarbon separation. Highly connected minimal edge-transitive derived and related nets, obtained via the deconstruction of nodes of the edge-transitive nets, are suitable blueprints and can potentially be deployed in the future ‘designed syntheses’ of MOFs. The further employment of the conceptual net-coded building units (e.g. highly connected MBBs and edge-transitive SBLs) in the practical reticular synthesis results in the rational design and construction of functional MOF platforms like shp-, alb-, kce-, kex- and eea- MOFs. In addition, the isoreticular synthesis of Al-cea-MOF-2 with functionalized pendant acid moieties inside pore channels in comparison to the parent Al-cea-MOF-1 led to enhanced light hydrocarbons separation performance. Moreover, controlling the molecular defects in Zr-fum-fcu-MOFs resulted in the development of an ultramicroporous adsorbent with an engineered aperture size for the highly efficient separation of butane/iso-butane.

Abstract: In this work, carbon molecular sieve (CMS) membranes were prepared based on a polymer of intrinsic microporosity, named PIM-6FDA-OH. The goal of this work was to examine the effect of the fabrication parameters of the CMS membranes on the gas separation performance of the final CMS membranes produced. Furthermore, the performance changes are reported for membranes physically aged over 7, 30, 60, and 90 days. The membranes prepared consisted of thin-film (about 3 !m thick) CMS selective layers supported by a stainless-steel tube. The experiments were split into four projects. The first project aimed to determine the effect the layer thickness had on the final performance of the produced CMS membranes. Five pairs of membranes were prepared using different coating solution concentrations, and different number of layers. The concentrations used were 5 (1 layer), 7.5 (1 layer), and 9 wt% (1, 2, and 3 layers) polymer in THF. The membranes had the same soak time of 15 minutes and pyrolysis temperature of 650 °C. The results showed that the increase in number of layers did not provide any benefits and was unnecessary. Moreover, the decrease in concentration produced membranes with higher permeances but with a greater loss in selectivity. Therefore, the 9 wt% concentration solution with one layer was chosen for the remaining experiments. The second project examined the effect of the pyrolysis temperature on the performance of the final membranes produced. All membranes were made with the 9 wt% solution and the soak time was held constant at 15 minutes. The soak temperatures tested were: 700, 750, 850, and 950. °C. The membranes pyrolyzed at temperatures above 650 °C were severely defective. This suggests that either the precursor polymer could not form defect-free thin membranes using high soak temperatures, or another potential reason is related to interfacial defect formation between the CMS layer and the porous stainless-steel support. Further experiments are required to fully understand the soak temperature effect on the formation of thin CMS films on porous supports. The third project examined the effect of the soak time (i.e. time the membranes are held isothermally at the pyrolysis temperature) on the final performance of the membranes. The same 9 wt% solution was used, and the pyrolysis temperature was 650 °C. The pyrolysis soak times were 15 minutes, 1 hour, 3 hours, and 10 hours, respectively. The results showed that as the soak time increased the membranes became denser and provided higher selectivities and lower permeances. Furthermore, the membranes with longer soak times became more size-sieving earlier during physical aging than the membranes made with shorter soak times. Physical aging was accelerated with an increase in soak time, i.e., membranes made by soaking over 10 hours reached stable permeance over time starting at day 7. The fourth project aimed to investigate the preparation process, as well as to test the performance of the membranes under different environments. Two types of polyimide precursor membranes were made, one set with the pristine polyimide and the other one with a PDMS top coating. The results showed that the membranes with PDMS had similar selectivities but far slower permeances than the CMS membranes, the membranes made without PDMS coating had much lower selectivities and permeances. CMS membranes soaked for 15 minutes and 3 hours, respectively, were tested to check the permeances of all the five gases (H2, O2, N2, CH4, and CO2) under pressure cycles from 2 to 8 bar. The membranes passed the tests and their permeances were not affected by exposing them to high pressures and back, except for the membranes soaked for 3 hours when tested with CO2.

No description available.

A thesis submitted for the degree of Doctor of Philosophy to The Department of Chemical and Metallurgical Engineering, Faculty of Engineering, University of the Witwatersrand, Johannesburg, 2016 / Separation of materials is crucial to the operation of the majority of chemical processes, not only for the purification of final products but also for the processing of feed-stocks prior to chemical reaction. The most commonplace method of materials separation is distillation which, unfortunately, is often an energy-intensive process and contributes significantly to mankind’s energy consumption and carbon dioxide emissions. Alternative approaches to separation are therefore a crucial element of the ongoing pursuit for sustainability in chemical industries. There are two principal ways of going about this. The first is to replace distillation units with alternative unit operations that can achieve the same separation with less energy expenditure. The second approach is overall flowsheet revision, fundamentally changing a separation cycle to minimize its energy requirements. The greatest improvements to energy efficiency will be achieved by applying both approaches in tandem. However, each must be developed separately to make that possible. This thesis lays the groundwork for radical revision of major separation operations by showcasing a new overall flowsheet for bioethanol separation that promises tremendous improvements in separation efficiency, reducing the energy usage involved in ethanol purification by as much as 40% in some scenarios. It also develops a novel method for the design of multi-membrane permeation units, showing how area ratio can be manipulated to fundamentally alter separation performance from such units, resulting in superior separation performance to conventional units, achieving higher recoveries than conventional setups. With membranes being an increasingly popular separation method, the potential for superior performance from multi-membrane units promises improvements in separation efficiency.

no / Research and technology innovations in the 1970s led to the significant commercial practice of gas separation by membranes that exists today. These advances involved developing membrane structures that could produce high fluxes and modules for packing a large amount of membrane area per unit volume (Murphy et al., 2009). At present, the share of using a polymeric membrane in the capture of CO2 is increasing and gradually the membrane technology is considered as the promising method in separation units, although the number of commercial membranes is not high. CO2 capture from natural gas is one of the controversial topics that many researchers and engineers try to find the best method satisfying both high efficiency and low capital cost. In common, chemical physical absorption towers are applied to remove CO2 from natural gas in order to prevent pipeline corrosion, even though the other component such as H2S gives rise to operating problems. The obscure angle of a conventional unit is related to the high energy consumption while the absorbent needs to be purified by the regeneration units which implement the temperature as a unique manipulating parameter for separating amine groups. The great advantages of using the membrane in gas industry are the low capital cost, easy installation and maintenance so that for this simple reason, new membranes come to the market for different types of processes. Capture of CO2 from natural gas accounts for one of the major difficulties so that the engineers try to employ membrane modules as to alter the process efficiency. However, there are only a limited number of membranes that can be used in real industry and the research still continues over this interesting topic (Burggraaf and Cot, 1996).

The objective of this study was to examine the effects of annealing polyimide-organosilicate hybrid membranes on gas transport. In addition, the effects of carbon dioxide pressure on the gas transport of unannealed polyimide-organosilicate hybrid membranes were evaluated. The membranes in both studies consisted of sol-gel derived organosilicate domains covalently bonded to a 6FDA-6FpDA-DABA polyimide using partially hydrolyzed tetramethoxysilane (TMOS), methyltrimethoxysilane (MTMOS) or phenyltrimethoxysilane (PTMOS). The first study subjected the hybrid membranes to a 400°C annealing process to enhance gas separation performance by altering the organosilicate structures. The hybrid membranes were evaluated before and after annealing using pure gases (He, O₂, N₂, CH₄, CO₂) at 35°C and a feed pressure of 4 atm. The permeability for most of the membranes increased 200-500% after the annealing process while the permselectivity dropped anywhere from 0 to 50%. The exceptions were the 6FDA-6FpDA-DABA-25 22.5 wt% TMOS and MTMOS hybrid membranes, both of which exhibited increases in the CO₂ permeability and CO₂-CH₄ permselectivity. The increase in permeation was attributed to increases in the free volume and enhanced segmental mobility of the chain ends resulting from the removal of sol-gel condensation and polymer degradation byproducts. For the second study, the transport properties of four membranes, 6FDA-6FpDA polyimide, 6FDA-6FpDA-DABA polyimide, MTMOS and PTMOS-based hybrid materials, were characterized as a function of feed pressure to evaluate how the hybrid materials reacted to CO₂ plasticization. Steady-state gas permeation experiments were performed at 35°C using pure CO₂ and CH₄ gases at feed pressures ranging from 4 to 30 atm. All four materials exhibited dual mode sorption up to feed pressures of 17 atm, at which point the effects of CO₂ plasticization were observed. / Master of Science