Polymeric membranes have been essential to increasing the efficiency of membrane separation processes. The viability of membrane systems for industrial gas applications lies in the tolerance of such membranes to contamination. While membrane contamination from volatile species can be addressed using purge streams and heat treatment, contamination from non-volatile hydrocarbons can cause a significant decline in membrane permselectivity. This study was focused on the characterization and remediation of cellulose acetate (CA) hollow fibre membranes contaminated by heavy hydrocarbons. CA membranes have a moderate resistance against performance decline from hydrocarbons found in natural gas. Hollow fibre CA membranes were coated with motor oil lubricant to simulate heavy hydrocarbon contamination from large-scale gas compressors and industrial feed streams, and remediation of the CA fibres was conducted using solvent extraction methods. The permeabilities of the membranes to carbon dioxide, helium, hydrogen, methane, nitrogen and oxygen were measured at pressures 300 – 1500kPa and at temperatures 25° – 50°C. It was shown that even a thin layer of oil on the membrane surface can result in substantial losses in membrane performance, with faster permeating gases (e.g. He and H₂) suffering the worst losses. Solvent exchange, in which the membrane was washed using a series of solutions of varying organic content, was unable to remediate the membrane effectively, while the removal of the heavy hydrocarbons by a direct cyclohexane rinse was found to work well to restore the membrane performance.

Membrane separations are rapidly growing alternatives to traditionally expensive gas separation processes. For natural gas purification, membranes are used to remove carbon dioxide to prevent pipeline corrosion and increase the heating value of the natural gas. The robust chemical and physical properties of polyimide membranes make them ideal for the numerous components and high pressures associated with natural gas production. Typically, the performance of membranes changes over time as a result of physical aging of the polymer. Previous work shows that the thin selective layer of an asymmetric hollow fiber membrane, the morphology of choice for gas separations, ages differently than a thick dense film of the same material. Also, carbon dioxide, which is highly soluble in most polymers, can actively swell and plasticize polymer membranes at higher pressures. In this work, free acid groups present in the model polyimide are covalently crosslinked to stabilize the matrix against plasticization. Physical aging of two different crosslinked derivatives are compared to the free acid polyimide through gas permeation, gas sorption, and refractive index measurements. Thick (~50 m) and thin (~650 nm) films are examined to determine the effects of sample dimension on physical aging. The crosslinking mechanism employs diol substituents to form ester linkages through the free acid group. However, the annealing treatment, above the glass transition temperature, used to "reset" the thermal history of the films is found to form a new crosslinked polymer. Characterization of this new crosslinking mechanism reveals a high-temperature decarboxylation of the free acid creates free-radical phenyl groups which form covalent crosslinks through other portions of the polymer structure. Since ester crosslinks may be vulnerable to hydrolysis in aggressive gas feed streams, this new mechanism of crosslinking may create a more robust membrane for aggressive separations. In addition to the physical aging study, supercritical carbon dioxide conditioning of the two glycol crosslinked polyimides is compared to the free acid polymer. In this case, the free acid polymer is not crosslinked since the esterification crosslinking reaction occurs at much lower temperature than the decarboxylation mechanism. The free acid polymer displays an atypical permeation response under supercritical carbon dioxide conditions which suggests a structural reorganization of the polymer occurs. The crosslinked polymers do not exhibit this type of response. Mixed gas permeation confirms a substantial decrease in the productivity of the free acid polyimide and reveals the enhanced stability of the crosslinked polyimides following the supercritical carbon dioxide conditioning. Finally, examination of structurally similar fluorine-containing polyimides following approximately 18 years of aging allows the study of polymer structure on physical aging. A 6FDA-based polyimide is compared to a BPDA-based polyimide to understand the effects of bulky, CF3 groups on physical aging, and polyimides with diamine isomers reveal the effects of structural symmetry on physical aging.

Thesis (Ph. D.)--Ohio State University, 2008.

Este trabalho tem por objetivo avaliar a viabilidade técnica de processos de separação de gás carbônico em correntes de gases de combustão. Neste sentido, a separação por meio de membranas e por criogenia são avaliadas por meio de simulação de sistemas. As propostas envolvendo membranas avaliam arranjos de membranas em série, os quais são otimizados para condições de maior fluxo permeado e maior beneficio econômico. A corrente de alimentação é de 5 kmol/s e as respectivas frações molares de CO2 e N2 que compõem esta corrente são 0,15 e 0,85. Os resultados obtidos da otimização, para um arranjo de três membranas em série de polyimida de 9000 m² de área superficial, foram uma corrente de permeado de 443,1 mol/s de CO2 a 41,6%, correspondendo a aproximadamente 59% do CO2 da corrente de alimentação. Já com um arranjo de 6 membranas de 9000 m², onde a função objetivo é o maior lucro, foi selecionado o material kapton e a quantidade de CO2 separada é 161,12 mol/s, cuja concentração na mistura é de 79%, e a função objetivo tem um valor de 24.405,30 €/ano. Na outra parte do trabalho, propõe-se e avalia-se um ciclo para o aproveitamento da disponibilidade térmica na regasificação do gás natural líquido, para liquefação de CO2. Obtém-se como resultando em CO2 líquido com fração molar igual a 94%. Este processo consta de uma corrente proveniente da combustão completa de 1 mol/s de metano, contendo 1 mol/s de CO2 e 7,52 mol/s de N2. Esta corrente é comprimida e resfriada até atingir a pressão de 4000 kPa e 25 °C, posteriormente uma membrana enriquece a corrente de gases de combustão, que novamente é comprimida e resfriada até se obter a condensação e separação do CO2. Realiza-se o cálculo de equilíbrio líquido-vapor da mistura utilizando as equações de Peng-Robinson e a regra de mistura de Van der Waals no software VRTherm. A vazão molar do CO2 líquido obtida é de 0,3207 mol/s na concentração declarada. A intensidade energética do processo é de 1,135 kWh/kg de CO2 liquefeito. / The objective of this work is to evaluate the technical feasibility of carbon dioxide separation processes of flue gases streams. In this way, separation processes due membrane and cryogenics are evaluated by system simulation. The systems using membranes evaluates setup of those membranes in series, these setups are optimized for the largest permeate molar flow and the largest economic profit. The feed stream is a 5 kmol/s CO2 – N2 mixture, with molar fraction of 0.15 and 0.85 respectively. The result obtained from the optimization for a setup of three polyimide membranes of 9000 m² is a permeate stream of 443.1 mol/s with CO2 at 41.6%, corresponding to aproximadely 59% of the CO2 contained in the feed stream. When a setup of six 9000 m² membranes is analyzed using an objective function that results in the largest profit, kapton was selected as the material for the membranes. The quantity of CO2 captured is 161.12 mol/s, at 79% of concentration in the mixture, and the objective function has a value of 24,405.30 €/year. The second part of this work, proposes and evaluates a cycle that takes the thermal availability of the regasification of liquid natural gas in advantage for CO2 liquefaction. The product of the cycle is liquid CO2, with a molar fraction of 0.94. The process is fed with a stream that comes from the stoichiometric combustion of 1 mol/s of methane, that stream is composed by 1 mol/s of CO2 and 7.52 mol/s of N2. The stream is then compressed up to the pressure of 4000 kPa and cooled down to 25 °C. After that a membrane concentrates the CO2 in one stream, which is again compressed and cooled down until the condensation of CO2 is achieved. Calculations of liquid – vapor are performed with the Peng- Robinson’s equations and the Van der Waals mixture rule using the software VRTherm. The molar flow rate of liquid CO2 obtained is of 0.3207 mol/s in the concentration mentioned before. The energy intensity of the process is of 1.135 kWh/kg of liquid CO2.

Este trabalho tem por objetivo avaliar a viabilidade técnica de processos de separação de gás carbônico em correntes de gases de combustão. Neste sentido, a separação por meio de membranas e por criogenia são avaliadas por meio de simulação de sistemas. As propostas envolvendo membranas avaliam arranjos de membranas em série, os quais são otimizados para condições de maior fluxo permeado e maior beneficio econômico. A corrente de alimentação é de 5 kmol/s e as respectivas frações molares de CO2 e N2 que compõem esta corrente são 0,15 e 0,85. Os resultados obtidos da otimização, para um arranjo de três membranas em série de polyimida de 9000 m² de área superficial, foram uma corrente de permeado de 443,1 mol/s de CO2 a 41,6%, correspondendo a aproximadamente 59% do CO2 da corrente de alimentação. Já com um arranjo de 6 membranas de 9000 m², onde a função objetivo é o maior lucro, foi selecionado o material kapton e a quantidade de CO2 separada é 161,12 mol/s, cuja concentração na mistura é de 79%, e a função objetivo tem um valor de 24.405,30 €/ano. Na outra parte do trabalho, propõe-se e avalia-se um ciclo para o aproveitamento da disponibilidade térmica na regasificação do gás natural líquido, para liquefação de CO2. Obtém-se como resultando em CO2 líquido com fração molar igual a 94%. Este processo consta de uma corrente proveniente da combustão completa de 1 mol/s de metano, contendo 1 mol/s de CO2 e 7,52 mol/s de N2. Esta corrente é comprimida e resfriada até atingir a pressão de 4000 kPa e 25 °C, posteriormente uma membrana enriquece a corrente de gases de combustão, que novamente é comprimida e resfriada até se obter a condensação e separação do CO2. Realiza-se o cálculo de equilíbrio líquido-vapor da mistura utilizando as equações de Peng-Robinson e a regra de mistura de Van der Waals no software VRTherm. A vazão molar do CO2 líquido obtida é de 0,3207 mol/s na concentração declarada. A intensidade energética do processo é de 1,135 kWh/kg de CO2 liquefeito. / The objective of this work is to evaluate the technical feasibility of carbon dioxide separation processes of flue gases streams. In this way, separation processes due membrane and cryogenics are evaluated by system simulation. The systems using membranes evaluates setup of those membranes in series, these setups are optimized for the largest permeate molar flow and the largest economic profit. The feed stream is a 5 kmol/s CO2 – N2 mixture, with molar fraction of 0.15 and 0.85 respectively. The result obtained from the optimization for a setup of three polyimide membranes of 9000 m² is a permeate stream of 443.1 mol/s with CO2 at 41.6%, corresponding to aproximadely 59% of the CO2 contained in the feed stream. When a setup of six 9000 m² membranes is analyzed using an objective function that results in the largest profit, kapton was selected as the material for the membranes. The quantity of CO2 captured is 161.12 mol/s, at 79% of concentration in the mixture, and the objective function has a value of 24,405.30 €/year. The second part of this work, proposes and evaluates a cycle that takes the thermal availability of the regasification of liquid natural gas in advantage for CO2 liquefaction. The product of the cycle is liquid CO2, with a molar fraction of 0.94. The process is fed with a stream that comes from the stoichiometric combustion of 1 mol/s of methane, that stream is composed by 1 mol/s of CO2 and 7.52 mol/s of N2. The stream is then compressed up to the pressure of 4000 kPa and cooled down to 25 °C. After that a membrane concentrates the CO2 in one stream, which is again compressed and cooled down until the condensation of CO2 is achieved. Calculations of liquid – vapor are performed with the Peng- Robinson’s equations and the Van der Waals mixture rule using the software VRTherm. The molar flow rate of liquid CO2 obtained is of 0.3207 mol/s in the concentration mentioned before. The energy intensity of the process is of 1.135 kWh/kg of liquid CO2.

Due to their high surface areas and structural tunability, porous metal-organic materials, MOMs, have attracted wide research interest in areas such as carbon capture, as the judicious choice of molecular building block (MBB) and linker facilitates the design of MOMs with myriad topologies and allows for a systematic variation of the pore environment. Families of MOMs with modular components, i.e. MOM platforms, are eminently suitable for targeting the selective adsorption of guest molecules such as CO2 because their pore size and pore functionality can each be tailored independently. MOMs with saturated metal centers (SMCs) that promote strong yet reversible CO2 binding in conjunction with favorable adsorption kinetics are an attractive alternative to MOMs containing unstaurated metal centers (UMCs) or amines. Whereas MOMs with SMCs and exclusively organic linkers typically have poor CO2 selectivity, it has been shown that a versatile, long known platform with SMCs, pillared square grids with inorganic anion pillars and pcu topology, exhibits high and selective CO2 uptake, a moderate CO2 binding affinity, and good stability under practical conditions. As detailed herein, the tuning of pore size and pore functionality in this platform has modulated the CO2 adsorption properties and revealed variants with unprecedented selectivity towards CO2 under industrially relevant conditions, even in the presence of moisture. With the aim of tuning pore chemistry while preserving pore size, we initially explored the effect of pillar substitution upon the carbon capture properties of a pillared square grid, [Cu(bipy)2(SiF6)] (SIFSIX-1-Cu). Room temperature CO2, CH4, and N2 adsorption isotherms revealed that substitution of the SiF62- (“SIFSIX”) inorganic pillar with TiF62- (“TIFSIX”) or SnF62- (“SNIFSIX”) modulated CO2 uptake, CO2 affinity (heat of adsorption, Qst), and selectivity vs. CH4 and N2. TIFSIX-1-Cu and SNIFSIX-1-Cu were calculated to exhibit the highest CO2/N2 and CO2/CH4 adsorption selectivites of the series, respectively. Modeling studies of TIFSIX-1-Cu and SIFSIX-1-Cu suggested that the enhancements in low pressure CO2 uptake and CO2 selectivity in the former arose from the stronger polarization of CO2 molecules by TIFSIX-1-Cu. The stronger framework-CO2 interaction at the primary binding site in TIFSIX-1-Cu correlates with the greater electronegativity of the pillar fluorine atoms relative to those in SIFSIX-1-Cu, and in turn to the higher polarizability of Ti4+ vs. Si4+. The effect of tuning pore size upon the carbon capture performance of pillared square grid nets was next investigated. Linker substitution afforded three variants, SIFSIX-2-Cu, SIFSIX-2-Cu-i, and SIFSIX-3-Zn, with pore sizes ranging from nanoporous (13.05 Å in SIFSIX-2-Cu) to ultramicroporous (3.84 Å in SIFSIX-3-Zn). Single-gas adsorption isotherms showed that SIFSIX-2-Cu-i, a doubly interpenetrated polymorph of SIFSIX-2-Cu with contracted pores (5.15 Å), exhibited far higher CO2 uptake, Qst towards CO2, and selectivity towards CO2 vs. CH4 and N2 than its non-interpenetrated counterpart. Further contraction of the pores afforded SIFSIX-3-Zn, a MOM with enhanced CO2 binding affinity and selectivity vs. SIFSIX-2-Cu-i. Remarkably, the selectivity of SIFSIX-3-Zn towards CO2 was found to be unprecedented among porous materials. Equilibrium and column breakthrough adsorption tests involving gas mixtures meant to mimic post-combustion carbon capture (CO2/N2), natural gas/biogas purification (CO2/CH4), and syngas purification (CO2/H2) confirmed the high selectivities of SIFSIX-2-Cu-i and SIFSIX-3-Zn. Gas mixture experiments also revealed that SIFSIX-3-Zn exhibited optimal CO2 adsorption kinetics. Most importantly, the CO2 selectivity of SIFSIX-2-Cu-i and SIFSIX-3-Zn was minimally affected in the presence of moisture. Modeling studies of CO2 adsorption in SIFSIX-3-Zn (experimental Qst ~ 45 kJ/mol at all loadings) revealed strong yet reversible electrostatic interactions between CO2 molecules and the SIFSIX pillars lining the confined channels of the material. Porous materials based upon the non-covalent assembly of discrete MBBs can also exhibit high surface areas and systematically tunable pore environments. Molecular porous material (MPM) platforms have begun to emerge despite the greater challenge of designing such materials in comparison to MOMs. Herein we report the tuning of pore functionality in an MPM platform based upon an extensive hydrogen-bonded network of paddlewheel-shaped [Cu(ade)4L2] complexes (ade = adenine; L = axial ligand). The substitution of Cl axial ligands with inorganic TIFSIX moieties has produced [Cu2(ade)4(TiF6)2], MPM-1-TIFSIX, a variant with enhanced CO2 separation performance and stability. Single-gas adsorption isotherms reveal that MPM-1-TIFSIX exhibits the highest CO2 uptake and CO2 Qst yet reported for an MPM as well as high selectivity towards CO2 vs. CH4 and N2. Modeling studies indicated strong electrostatic interactions between CO2 and the TIFSIX ligands lining the pores of MPM-1-TIFSIX. In addition to dramatically surpassing MPM-1-Cl with regard to CO2 separation performance, MPM-1-TIFSIX exhibits thermal stability up to 568 K and retains its performance even after immersion in water for 24 hrs. Comprehensively, the results presented herein affirm that porous materials featuring inorganic anions and SMCs can exhibit high and selective CO2 uptake, sufficient stability, and facile activation conditions without the drawbacks associated with UMCs and amines, i.e. competitive water adsorption and high regeneration energy, respectively.

Abstract Gas removal from the papermaking process is currently a standard practice, whereas purification of the internal water circulation has become common only recently. Both unit processes have progressed greatly during recent decades and new concepts are constantly being developed. The aim of this thesis was to analyse the efficiency and applicability of a channel flow design introduced by Metso for passive white water deaeration and to study the dynamics of passive bubbly gas removal. In addition, separation of the detrimental process water components by selective flotation during deaeration was studied to add further functionality to the channel flow design. Turbulent mixing at the flow discharge and the consequent air entrainment were seen to limit the gas separation efficiency. Also, the properties of different white waters notably affect their deaeration through viscous forces, the concentration of surface active components and bubble-particle interactions. Thus similar levels of gas separation cannot be achieved with all process waters. The analysis showed that the drag of small microbubbles is mostly caused by hydrophobic contamination and the dispersed particles that readily attach to the bubbles. Correlations were derived based on experimental data to provide new information on the drag force experienced by small bubbles in white waters. Chemically unaided flotation of white water in the channel flow was shown to be efficient in separating hydrophobic contaminants that have adverse effects on paper machine production and product quality. Both good reductions in contaminant content and high selectivity in their removal were achieved. Channel flow with an overflow can be considered well suited for the first stage of froth separation, while further treatment of the channel flow reject may consist of a secondary flotation or other process that enables the recirculation of fines and fillers. Although a certain level of losses of fines and fillers must be expected, substantial fraction of these solid components can be returned to the process stream. The proposed multifunctional process, channel flow deaeration and frothing of white water, was seen to be straightforward, economical and feasible while also providing benefits in terms of total process efficiency that are not delivered by any current process scheme. The experimental parameters presented here regarding bubble dynamics and flotation efficiency can be used to achieve better models of these processes.

Zeolite membranes have great potential in gas separation applications because of their unique selective properties. The main challenge is in synthesizing defect-free zeolite membranes. In this study, we synthesized silicalite-1 zeolite membranes on ceramic supports composed of Al2O3 and TiO2 using the pore-plugging method. We investigated the effect of the fill-level in the autoclave during the synthesis on the membrane performance. In particular, we were interested in determining the conditions at which the defects' contribution to the total transport is minimized. We adopted and further developed the approach proposed by Carter (2019) to quantify the permeance contribution through defects. Comparing the membrane performance before and after calcination, we proposed several modifications to the original analysis of Carter (2019). Knowing the defect transport contribution, we determined the corrected diffusivity, an intrinsic property of zeolite crystals at a given temperature, of several adsorbed gases on silicalite-1 crystals. The defect's contribution decreased as the autoclave fill-level increased from 94 to 98%. A further increase in the autoclave fill-level introduced more defects and caused the autoclave lid to rupture. Despite the differences in the membranes' performance arising from the autoclave fill-level, the corrected diffusivities of CO2, CH4, and N2 in silicalite-1 showed minimal variation from membrane to membrane. This proves the validity of the proposed characterization method. Moreover, the reported corrected diffusivities are comparable to the literature's values, found using other characterization methods. However, none of the previously used methods is as simple and straightforward as the one we further developed in this study.

La séparation CO2/N2 et H2/CO2 permet de limiter le rejet de CO2 dans l’atmosphère issu des gaz industriels et les membranes présentent de nombreux avantages tant sur le plan économique que pratique. Les membranes polymère sont faciles à mettre en forme mais un compromis entre perméabilité et sélectivité doit généralement être trouvé : pour améliorer les performances, des membranes à matrice mixte (MMM) incorporant des MOFs (matériaux hybrides poreux cristallisés) dispersés dans la phase polymère ont été proposées. A la différence des matériaux poreux inorganiques, les MOFs ont une meilleure compatibilité avec la matrice polymère du fait de leur caractère hybride organiqueinorganique. Dans le cadre de cette thèse, des polycarboxylates de Fe3+ et Al3+ poreux, stables à l’eau, et possédant de bonnes propriétés d’adsorption sélective du CO2 ont été synthétisés en milieu aqueux et mis à l’échelle de quelques grammes. Deux nouveaux polycarboxylates de Fe3+ poreux fonctionnalisés par des fonctions -COOH libres ont été obtenus à température ambiante. Pour l’un d’entre eux, la structure a été déterminée par diffraction des rayons X. Une deuxième partie de la thèse a été consacrée à la synthèse de nanoparticules de MOFs avec un bon rendement. Une partie importante de ce travail a porté sur le contrôle de la taille et la morphologie des nanoparticules de MIL-96(Al). Ce travail a conduit à la préparation de MMMs à base de MIL-96(Al) dont les performances sont supérieures à la membrane pure polymère pour la séparation CO2/N2. La dernière partie de ce travail de thèse a porté sur l’étude physico-chimique de la compatibilité entre le ZIF-8 et deux polymères (PVA et PIM-1). Ce travail a consisté à effectuer une caractérisation complète de solutions colloïdales MOFs/polymère en couplant plusieurs techniques (DLS, TEM, SAXS). Cette étude a montré que la compatibilité MOF/polymère est très dépendante de la chimie de surface des MOFs et des propriétés physico-chimiques du polymère (rigidité, caractère hydrophile/hydrophobe…). / CO2 capture and storage (CCS) is of high economical and societal interest. CO2/N2 andH2/CO2 separations are able to limit atmospheric CO2 emissions produced by industrial exhausts andmembranes present numerous economical and practical advantages. Polymer membranes are easy toprocess and possess interesting mechanical properties. However, there is a trade-off to make betweenpermeability and selectivity. Mixed-matrix membranes (MMM) based on MOFs (porous crystallinehybrid materials) have been proposed to boost the performances of polymer membranes for CO2capture. In comparison to other inorganic porous materials, one may expect that the compatibilitybetween MOFs and polymers is enhanced due to the hybrid character of MOFs.In this work, porous water stable polycarboxylate MOFs based on Fe3+ and Al3+ with promisingproperties for CO2 adsorption were synthesized for large-scale production using water as the mainsolvent. Two new porous polycarboxylate Fe3+ MOF bearing free -COOH groups in the frameworkwere obtained at room temperature as nanoparticles. The crystallographic structure of one of thesematerials was determined by single crystal X-ray diffraction. A second part of the thesis was devotedto the synthesis of MOFs nanoparticles with good yield. We focused our attention on the control of thediameter and morphology of MIL-96(Al) nanoparticles. This study led to the preparation of MMMsbased on MIL-96(Al) with promising properties for CO2/N2 separation. Finally, the compatibilitybetween MOF particles and polymers was studied for two systems (ZIF-8/PIM-1 and ZIF-8/PVOH),showing the influence of the surface chemistry of MOFs and the physico-chemical properties ofpolymer on the matching between MOFs and polymers.

No description available.