The focus of this research project was to develop a fundamental understanding of the structure-gas transport property relationship in Nafion® to investigate its potential use as a gas separation membrane material for natural gas (NG) applications including carbon dioxide removal from NG, helium recovery, higher-hydrocarbon removal, and nitrogen separation from methane. Separation processes account for ~45% of all energy used in chemical plants and petroleum refineries. As the drive for energy savings and sustainability intensifies, more efficient separation technology becomes increasingly important. Saudi Arabia ranks among the world’s top 5 NG producers. Commercial hydrocarbon-based glassy polymers often lose their gas separation properties in the presence of condensable, highly sorbing NG components such as CO2, ethane, propane, n-butane, and C5+ hydrocarbons. This deterioration in gas separation performance results from penetrant-induced dilation and plasticization of the polymer matrix, leading to significant methane and higher hydrocarbon losses. Polymers that have intrinsically low affinity to high-solubility NG components may be less susceptible to plasticization and therefore offer better performance under actual field conditions. By virtue of their strong carbon-fluorine bonds and chemical inertness, perfluoropolymers exhibit very low affinity for hydrocarbon gases. Nafion®, the prototypical perfluoro-sulfonated ionomer, comprising hydrophilic sulfonate groups phase-separated from a hydrophobic perfluorocarbon matrix, has demonstrated interesting permeability and selectivity relationships for gas pairs relevant to NG applications. Gas transport properties of Nafion® indicated gas solubility behavior similar to rubbery polymers but with sieving properties more commonly observed in low free volume glassy polymers. Nafion® demonstrated very low solubility for CO2 and hydrocarbon gases; the trend-line slope of solubility versus penetrant condensability in Nafion® was almost 2.5 times lower than that of typical hydrocarbon polymers, highlighting Nafion’s® effectiveness in resisting high-solubility induced plasticization. Additionally, Nafion® showed extraordinarily high permselectivities between small gases (He, H2, CO2) and large hydrocarbon gases (C1+): He/CH4 = 445, He/C3H8 = 7400, CO2/CH4 = 28, CO2/C3H8 = 460, H2/CH4 = 84 and H2/C3H8 = 1400 owing to its tightly packed chain domains. These high selectivities could potentially be harnessed for helium recovery and CO2 removal in natural gas applications, and hydrogen recovery from refinery gas streams. Pressure-dependent pure- and mixed-gas permeabilities in Nafion® were determined at 35 °C. Nafion® demonstrated two divergent pressure-dependent permeability phenomena: gas compression and plasticization. In pure-gas experiments, the permeability of the permanent gases H2, O2, N2 and CH4 decreased with increasing pressure due to polymer compression, whereas the permeability of the more condensable gases CO2, C2H6 and C3H8 increased dramatically due to solubility-induced plasticization. Binary CO2/CH4 (50:50) mixed-gas experiments showed reduced performance with up to 2-fold increases in CH4 permeability from 0.075 to 0.127 Barrer, and a 45% drop in selectivity (from 26 to 14), between 2 and 36 atm total pressure as a result of CO2-induced plasticization. At a typical NG CO2 partial pressure of 10 atm, Nafion® exhibited 24% lower CO2/CH4 selectivity of 19, with a 4-fold lower CO2 permeability of 1.8 Barrer relative to a commercial cellulose acetate (CA) membrane. Ternary CO2/CH4/C3H8 (30:50:20) experiments quantified the effect of CO2 and C3H8 plasticization. The presence of C3H8 reduced CO2 permeability further due to a competitive sorption effect causing a 31% reduction in CO2/CH4 selectivity, relative to its pure-gas value of 29, at 16 atm total feed pressure. The strong cation-exchanging sulfonate groups in Nafion® provided an opportunity to tailor the material properties by incorporating metal ions through a simple ion-exchange process. Nafion® neutralized with Fe3+ was investigated as a potential approach to mitigate CO2-plasticization. XRD results demonstrated an increase in crystallinity from 9% in Nafion H+ to 23% in Nafion Fe3+; however, no significant changes in the average inter chain spacing was observed. Raman and FT-IR technique qualitatively measured the strength of the ionic bond between Fe3+ cation and sulfonate anion. The strong crosslinking effect in Fe3+-cation-exchanged membrane demonstrated substantial increase in permselectivity: N2/CH4 selectivity increased by 39% (from 2.9 to 4.0) and CO2/CH4 selectivity increased by 25% (from 28 to 35). Binary CO2/CH4 (50:50) mixed-gas experiments at total feed pressures up to 30 atm quantified the effect of CO2 plasticization on the CO2/CH4 separation performance. Nafion® Fe3+ demonstrated better resistivity to plasticization enduring approximately 30% CH4 permeability increases from 0.033 Barrer at 2 atm to 0.043 Barrer at 15 atm CO2 partial pressure. At 10 atm CO2 partial pressure, CO2/CH4 selectivity in Nafion® Fe3+ decreased by 28% to 28 from its pure-gas value of 39, which was a significant improvement compared to Nafion® H+ membrane that decreased by 42% to 19 from its pure-gas value of 32.

In this dissertation the gas permeation process within four hybrid inorganic-organic membranes is modeled at the micro level using molecular dynamics (MD) and at the meso scale level using a diffusion mechanism. The predicted permeances and relative selectivity of CO₂ and CH₄ are compared with the experimental results. In the MD simulation a single-pore silica crystal framework model with and without inserted phenyl groups are used to define two membrane structures. We designate the two cases as PSPM and SPM respectively. To mimic the diffusion of gas across the membrane, a three-region system with a repulsive wall potential on the edge is employed. Results from the SPM model indicate that the pore size affects the permeance but not the selectivity. In the PSPM model the permeance decreases significantly when the pore size is below a critical value. The extent of decrease varies with the type of gas and this is reflected in the large selectivity in the PSPM model. When the initial diameter is 0.4 nm the model shows a selectivity of 17.3, which is very close to experimental results. At this selectivity the CO₂ permeance is 2.87 Ã 10^-4 mol m⁻²s⁻¹Pa⁻¹ and the CH₄ permeance is 1.66 Ã 10⁻⁵ mol m⁻²s⁻¹Pa⁻¹. For different gases we also studied the motions of the phenyl groups in the pore during the permeation process. The results show that in CO₂ diffusion the phenyl groups moves in a larger range than in CH₄ diffusion. The density profile of gas molecules that the phenyl groups see is analyzed using double layer phenyl groups . The results show that the number of phenyl groups cannot affect the permeation. In the meso scale study a mixed mechanism model with a grid framework is developed to model the permeation process. In the model the membrane is assumed to consist of various grids which follow three major diffusion mechanisms. Models with different grid sizes are employed for the four membranes. Parameters in each model are estimated from the permeance results of the two gases. By comparing the estimated parameters in the surface diffusion mechanism with the reported values, the acceptable grid models are determined and the models with the minimum number of grids are studied. The diffusion is dominated by the activated Knudsen diffusion mechanism at lower temperatures and follows the surface diffusion mechanism when the temperature is above a critical value. In the diffusion of both gases within the four membranes the surface diffusion portion is very close but the activated Knudsen diffusion portion is not. This explains why the permeation with high selectivity occurs at lower temperatures. By comparing the results it shows the two studies can validate each other. On the other hand the two methods can be complementary as the diffusion model is able to predict the permeance within the right range and the MD model is able to predict the selectivity more accurately. / Ph. D.

Membrane-based gas separation processes are an area of interest owing to their high industrial demand for a wide range of applications, such as natural gas purification from CO2 or H2, and N2 or O2 separation from air. This thesis is focused on developing and investigating polymeric-based membranes. Firstly, novel mixed matrix membranes (MMMs) were prepared, incorporating few-layer graphene in the polymer of intrinsic microporosity PIM-1. Secondly, novel polyphenylene-based polymers of intrinsic microporosity (PP-PIMs) were synthesised. An optimum preparation method of graphene/PIM-1 MMMs (GPMMMs) was established from numbers of experiments. In this study, graphene exfoliation was a step towards GPMMM preparation. Starting from graphene exfoliation in chloroform, as a good solvent for PIM-1, enhancement in graphene dispersibility was obtained with addition of PIM-1. This result helped in GPMMM preparation with high graphene content (up to 4 wt.%). Characterizations techniques such as Raman spectroscopy and scanning electron microscopy (SEM) of GPMMMs, confirmed the few layer graphene content, with morphology changes in the polymeric matrix compared to pure PIM-1.Gas permeability results of GPMMMs showed an enhancement in permeability with low loading graphene (0.1 wt.%) using a relatively low permeability PIM-1 batch, due to high water content. However, less influence of graphene incorporation on permeability was observed with a highly permeable PIM-1 batch. Reduction in permeability over time, termed an ageing effect, is known for a polymer of high-free volume like PIM-1. However, the enhancement of GPMMMs permeability after eight months storage was shown to be retained. Novel PP-PIMs were prepared from novel precursors using a series known organic reactions. PP-PIMs were divided into two groups of polymers based on their polymerization reactions. A group of polymers were prepared from condensation polymerization between bis-catecol monomers and tetrafluoroterephthalonitrile (TFTPN). Another group of polymers were prepared from Diels Alder polymerization between monomers of terminal bisphenylacetylene groups and bis tetraphenylcyclopentadienones (TPCPDs). All of which yielded polymers with apparent BET surface area in the range 290-443 m2 g-1.

High energy consumption is a crucial challenge in gas separation processes. With current energy intensive separation methods, there is a real need for more energy-efficient alternative technologies. Membrane technology demonstrates potential uses in industrial separation processes due to its potential energy efficiency, environmental friendliness, and small footprint. The continuous developments in material science contributed directly in enhancing the membrane performance through several engineering modifications such as thermal annealing, which presented visible improvements in gas permeation properties. The objective of this project was to investigate the thermal annealing of three fluorinated polymers (PAE1, PAE2, and TFMPD), aiming for favorable changes in gas permeation properties. In particular, each polymer was annealed for 3 h at various temperature values, targeting the intermediate stage, which is the zone where degradation started but a pure carbon structure stage was not formed yet. Overall, the thermal annealing study revealed that TFMPD had highest pure-gas separation performance among other polymers, in which the Robeson plots displayed that treated sample at 500 ºC surpassed the 2015 H2/CH4 upper bound, whereas the treated sample at 550 ºC surpassed 2019 upper bound of both CO2/CH4 and CO2/N2. Therefore, TFMPD can be a potential candidate polymer for membrane-based gas separation, especially for CO2 and H2 applications. This performance could be attributed to the internal structural changes in the polymer that occurred during thermal annealing. Hence, several characterization techniques were performed to detect these changes. For instance, it was realized that all polymers started crosslinking upon the thermal treatment at 350 ºC. Moreover, FTIR analysis indicated the release of several functional groups from treated polymers at high temperature values. Raman spectroscopy also confirmed that the observed substantial enhancement in gas permeation of annealed TFMPD at 550 ºC was due an early-stage carbon structure formation. Furthermore, several recommendations are proposed to continue the work in this project, which could lead to potential success of the thermally annealed polymers tested in this study in membrane-based gas separations applications.

Characterization of semi-permeable films promotes the systematic selection of membranes and process design. When acquiring the diffusive and sorption properties of gas transport in non-porous membranes, the time lag method is considered the conventional method of characterization. The time lag method involves monitoring the transient accumulation of species due to permeation on a fixed volume present in a downstream reservoir. In the thesis at hand, an alternative approach to the time lag technique is proposed, termed as the short cut method. The short cut method appoints the use of a two reservoir system, where the species decay in the upstream face of the membrane is monitored, in combination with the accumulation on the downstream end. The early and short time determination of membrane properties is done by monitoring the inflow and outflow flux profiles, including their respective analytical formulas. The newly proposed method was revealed to have estimated the properties at 1/10 the required time it takes for the classical time lag method, which also includes a better abidance to the required boundary conditions. A novel design of the upstream reservoir, consisting of a reference and working volume, is revealed, which includes instructional use, and the mechanics involved with its operation. Transient pressure decay profiles are successfully obtained when the reference and working volumes consisted of only tubing. However when tanks were included in the volumes, large errors in the decay were observed, in particular due to a non-instantaneous equilibration of the pressure during the start up. This hypothesis was further re-enforced by examining different upstream tank-based configurations. iii In the end, a validated numerical model was constructed for the purpose of simulating the two reservoir gas permeation system. A modified form of the finite differences scheme is utilized, in order to account for a concentration-dependent diffusivity of penetrants within the membrane. Permeation behavior in a composite membrane system was disclosed, which provided a new perspective in analyzing the errors associated with the practical aspect of the system.

Characterization of semi-permeable films promotes the systematic selection of membranes and process design. When acquiring the diffusive and sorption properties of gas transport in non-porous membranes, the time lag method is considered the conventional method of characterization. The time lag method involves monitoring the transient accumulation of species due to permeation on a fixed volume present in a downstream reservoir. In the thesis at hand, an alternative approach to the time lag technique is proposed, termed as the short cut method. The short cut method appoints the use of a two reservoir system, where the species decay in the upstream face of the membrane is monitored, in combination with the accumulation on the downstream end. The early and short time determination of membrane properties is done by monitoring the inflow and outflow flux profiles, including their respective analytical formulas. The newly proposed method was revealed to have estimated the properties at 1/10 the required time it takes for the classical time lag method, which also includes a better abidance to the required boundary conditions. A novel design of the upstream reservoir, consisting of a reference and working volume, is revealed, which includes instructional use, and the mechanics involved with its operation. Transient pressure decay profiles are successfully obtained when the reference and working volumes consisted of only tubing. However when tanks were included in the volumes, large errors in the decay were observed, in particular due to a non-instantaneous equilibration of the pressure during the start up. This hypothesis was further re-enforced by examining different upstream tank-based configurations. iii In the end, a validated numerical model was constructed for the purpose of simulating the two reservoir gas permeation system. A modified form of the finite differences scheme is utilized, in order to account for a concentration-dependent diffusivity of penetrants within the membrane. Permeation behavior in a composite membrane system was disclosed, which provided a new perspective in analyzing the errors associated with the practical aspect of the system.

Nanoporous molecular sieve materials like metal organic frameworks (MOFs) and metal oxide nanotubes (AlSiNTs) have found a wide range of technological applications in catalysis, separations, and ion exchange due to their salient features over other contemporary sensing materials. As a result, these materials can function as a chemical recognition layer that relies on analyte adsorption and they have shown to selectively adsorb specific gas molecules from mixtures. The characterization of gas adsorption in these materials is performed predominantly by commercial gravimetric equipment, whose capital and operating costs are generally high and require relatively large amounts of sample. Thus, it is desirable to obtain a reliable measure of the gas transport properties of these materials over a substantial range of pressure and temperature by non-gravimetric methods. The objective of this thesis is to investigate the adsorption and diffusion characteristics of recently-identified nanoporous materials through the development and use of a high-pressure/high-temperature quartz crystal microbalance (QCM) device. In this regard, this thesis is divided into four main objectives, viz. (1) Design and development of high temperature/ high pressure QCM device, (2) Measurement and analysis of adsorption characteristics in nanoporous materials, (3) Diffusion measurement and analysis in polymer thin films and (4) Diffusion measurement and analysis in MOF crystals. The results obtained in Objectives 2-4 will allow us to make important recommendations regarding the use of specific nanoporous materials in molecular separation applications and also lead to significant understanding of gas uptake thermodynamics in nanoporous materials via the application of analytical models to the experimental data.

Zeolite membranes are considered to be a promising alternative to polymeric membranes and they have the potential to separate gases under harsh conditions. Silicalite-1 membranes in particular are easy to prepare and suitable for several industrial applications. In this research project, silicalite-1/ceramic composite membranes were prepared using the pore plugging hydrothermal synthesis method and supports with zirconium oxide and/or titanium oxide as active layers. The effect of the support’s pore size on the morphology and permeation performance of the prepared membranes was investigated using five supports with different active layer pore sizes in the range of 0.14 – 1.4 m. The prepared membranes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), electron diffraction spectrometer (EDS), single gas and binary gas mixtures permeation tests. The results confirmed the presence of a typical silicalite-1 zeolite structure with a high internal crystalline order grown inside the pores of the active layer of the supports, with a dense film covering most of the supports active layers. Silicalite-1 crystals in the prepared membranes were preferably oriented with either a- or b-axes perpendicular to the support surface. Single gas permeation results illustrated that the observed permeances were not directly related to the kinetic diameter of permeants. Instead, the transport of the studied gases through the prepared membranes occurred by adsorption followed by surface diffusion mechanism. Binary gas tests performed with CO2 and N2 mixtures showed that the prepared membranes were selective and very permeable with CO2/N2 permselectivities up to 30 and a CO2 permeances in the order of 10-6 mol m-2 Pa-1 s-1. A model was developed, based on Maxwell−Stefan equations and Extended Langmuir adsorption isotherm, to describe the transport of binary CO2 and N2 mixtures through the prepared silicalite-1 membranes. The model results showed that the exchange diffusivities (D12 and D21) were less dependent on the feed pressure and feed composition compared to the permeances and the permselectivities. Hence, they are more appropriate to characterize the intrinsic transport properties of the prepared silicalite-1 membranes.

Characterization of semi-permeable films promotes the systematic selection of membranes and process design. When acquiring the diffusive and sorption properties of gas transport in non-porous membranes, the time lag method is considered the conventional method of characterization. The time lag method involves monitoring the transient accumulation of species due to permeation on a fixed volume present in a downstream reservoir. In the thesis at hand, an alternative approach to the time lag technique is proposed, termed as the short cut method. The short cut method appoints the use of a two reservoir system, where the species decay in the upstream face of the membrane is monitored, in combination with the accumulation on the downstream end. The early and short time determination of membrane properties is done by monitoring the inflow and outflow flux profiles, including their respective analytical formulas. The newly proposed method was revealed to have estimated the properties at 1/10 the required time it takes for the classical time lag method, which also includes a better abidance to the required boundary conditions. A novel design of the upstream reservoir, consisting of a reference and working volume, is revealed, which includes instructional use, and the mechanics involved with its operation. Transient pressure decay profiles are successfully obtained when the reference and working volumes consisted of only tubing. However when tanks were included in the volumes, large errors in the decay were observed, in particular due to a non-instantaneous equilibration of the pressure during the start up. This hypothesis was further re-enforced by examining different upstream tank-based configurations. iii In the end, a validated numerical model was constructed for the purpose of simulating the two reservoir gas permeation system. A modified form of the finite differences scheme is utilized, in order to account for a concentration-dependent diffusivity of penetrants within the membrane. Permeation behavior in a composite membrane system was disclosed, which provided a new perspective in analyzing the errors associated with the practical aspect of the system.

The effect of seeding on the properties of alumina supported MFI membranes was investigated in this study. Membranes were synthesized from clear solutions with a molar batch composition of TPAOH:9.80SiO2:0.025NaOH:0.019Al2O3: 602.27H2O:39.16C2H5OH on bare and seeded alumina supports at 130oC in autoclaves. The amount of seed on the support surface was changed between 0.6 mg/cm2 and 6.9 mg/cm2 by vacuum seeding method, which provided uniform and closely packed seed layers. Membranes were characterized by XRD and SEM, and by measuring single gas permeances of N2, SF6, n-C4H10 and i-C4H10. The quality of membranes was evaluated on the basis of N2/SF6 ideal selectivity. Membranes, which showed N2/SF6 ideal selectivity higher than 40, were considered to be good quality, comprising few defects. Good quality membranes were also used to separate butane isomers. Membranes synthesized on seeded supports had compact and uniform MFI layer if the seed amount is less than 1.0 mg/cm2 on the support surface. Membranes that were synthesized on the supports coated with higher amount of seed crystals showed an asymmetric structure with a dense and uniform MFI layer at the top, the support at the bottom and a seed layer between. Half of the membranes synthesized on seeded supports had N2/SF6 ideal selectivity higher than 40. These membranes exhibited n-C4H10/i-C4H10 separation selectivities between 5 and 27 and 8 and 21 at room temperature and at 200oC, respectively. High ideal and separation selectivities showed that membranes did not include non-zeolitic pores. Membranes synthesized on bare support had non-uniform MFI layer. Those membranes showed N2/SF6 ideal selectivities below Knudsen selectivity, indicating the existence of large non-zeolitic pores in the MFI layer.