Modification of ABS Membrane by PEG for Capturing Carbon Dioxide from CO2/N2 Streams

Carbon dioxide capture and storage (CCS) has been propounded as an important issue in greenhouse gas emissions control. In this connection, in the present article, the advantages of using polymeric membrane for separation of carbon dioxide from CO₂/N₂ streams have been discussed. A novel composition for fabrication of a blend membrane prepared from acrylonitrile-butadiene-styrene (ABS) terpolymer and polyethylene glycol (PEG) has been suggested. The influence of PEG molecular weight (in the range of 400 to 20000) on membrane characteristics and gas separation performance, the effect of PEG content (0–30 wt%) on gas transport properties, and the effect of feed side pressure (ranging from 1 to 8 bar) on CO₂ permeability have been studied. The results show that CO₂ permeability increases from 5.22 Barrer for neat ABS to 9.76 Barrer for ABS/PEG20000 (10 wt%) while the corresponding CO₂/N₂ selectivity increases from 25.97 to 44.36. Furthermore, it is concluded that this novel membrane composition has the potential to be considered as a commercial membrane.     

Mechanistic understanding of CO2-induced plasticization of a polyimide membrane: A combination of experiment and simulation study

Experimental measurements and fully atomistic simulations are carried out to examine the CO₂-induced plasticization of a polyimide membrane synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4′-oxydianiline (ODA). With increasing feed pressure, the permeability of CO₂ in the 6FDA-ODA membrane initially decreases, crosses a minimum, and then increases. The plasticization pressure is estimated to be at approximately 8 atm. The radial distribution functions between CO₂ and polyimide atoms reveal that the imide groups are the preferential sorption sites, followed by the ether and CF₃ groups. The experimental and simulated sorption isotherms of CO₂ are in fairly good agreement. At low loadings, CO₂ molecules are largely trapped with small mobility. With increasing loading, the polyimide membrane exhibits a depressed glass transition temperature, a dilated volume and an increased fractional free volume. In addition, larger and more interconnected voids appear and the mean radius of voids increases from 2.5 to 3.3 Å with increasing CO₂ loading. Consequently, the mobility of both CO₂ molecules and polymer chains is enhanced. Based on molecular displacement, the percentages of three types of motions (jumping, trapped, and continuous) are estimated for CO₂ in the membrane. The continuous motion contributes predominantly to CO₂ diffusion. At a high loading, the ether groups in the polyimide chains exhibit a significant effect on plasticization. It is therefore suggested that the plasticization could be suppressed by substituting the ether groups. The microscopic information of this study is particularly useful for the quantitative understanding of plasticization.     

High-pressure sorption isotherms and sorption kinetics of CH4 and CO2 on coals

Using a manometric experimental setup, high-pressure sorption measurements with CH₄ and CO₂ were performed on three Chinese coal samples of different rank (VR_r = 0.53%, 1.20%, and 3.86%). The experiments were conducted at 35, 45, and 55 °C with pressures up to 25 MPa on the 0.354-1 mm particle fraction in the dry state. The objective of this study was to explore the accuracy and reproducibility of the manometric method in the pressure and temperature range relevant for potential coalbed methane (CBM) and CO₂-enhanced CBM (CO₂-ECBM) activities (P > 8 MPa, T > 35 °C). Maximum experimental errors were estimated using the Gauss error propagation theorem, and reproducibility tests of the high-pressure sorption measurements for CH₄ and CO₂ were performed. Further, the experimental data presented here was used to explicitly study the CO₂ sorption behaviour of Chinese coal samples in the elevated pressure range (up to 25 MPa) and the effects of temperature on supercritical CO₂ sorption isotherms.The experiments provided characteristic excess sorption isotherms which, in the case of CO₂ exhibit a maximum around the critical pressure and then decline and level out towards a constant value. The results of these manometric tests are consistent with those of previous gravimetric sorption studies and corroborate a crossover of the 35, 45, and 55 °C CO₂ excess sorption isotherms in the high-pressure range. The measurement range could be extended, however, to significantly higher pressures. The excess sorption isotherms tend to converge, indicating that the temperature dependence of CO₂ excess sorption on coals at high-pressures (>20 MPa) becomes marginal. Further, all CO₂ high-pressure isotherms measured in this study were approximated by a three-parameter excess sorption function with special consideration of the density ratio of the “free” phase and the sorbed phase. This function provided a good representation of the experimental data.The maximum excess sorption capacity of the three coal samples for methane ranged from 0.8 to 1.6 mmol/g (dry, ash-free) and increased from medium volatile bituminous to subbituminous to anthracite. The medium volatile bituminous coal also exhibited the lowest overall excess sorption capacity for CO₂. However, the subbituminous coal was found to have the highest CO₂ sorption capacity of the three samples. The mass fraction of adsorbed substance as a function of time recorded during the first pressure step was used to analyze the kinetics of CH₄ and CO₂ sorption on the coal samples. CO₂ sorption proceeds more rapidly than CH₄ sorption on the anthracite and the medium volatile bituminous coal. For the subbituminous coal, methane sorption is initially faster, but during the final stage of the measurement CO₂ sorption approaches the equilibrium value more rapidly than methane.     

Gas transport in polymer membrane at temperatures above and below glass transition point

The processes of gas sorption and permeation in a polymer membrane at temperatures above and below the glass-transition point were examined using poly-4-methylpentene-1 (glass-transition temperature reported to be 40°C) as a membrane material. The permeabilities to O₂ and N₂ were independent of applied gas pressure at every temperature; the mean permeability coefficient to CO₂ increased with increasing gas pressure. The logarithm of the mean permeability coefficient to CO₂ increased linearly with gas pressure due to the plasticization effect induced by sorbed CO₂. From the sorption isotherms for CO₂ at 20 and 30°C it was judged that the glass transition was brought about by sorbed CO₂ at temperatures below the glass-transition point of the pure polymer. © 1994 John Wiley & Sons, Inc.     

Separation of CO2 and N2 on Zeolite Silicalate-1 Membrane Synthesized on Novel Support

This paper reports on the properties of an MFI-type zeolite (silicalite-1) membrane synthesized on a novel tubular support with a 0.45 µm-pore size active layer consisting of zirconium and titanium oxides. Even though the membrane was synthesized by a pore plugging method, apart from penetrating into the support, the silicalite-1 crystals formed a 1.5 µm layer on top of the support. After the zeolite synthesis, the Si constituted more than 35% of the active layer of the support, which implies small size and close packing of the silicalite-1 crystals in the pores of the active layer.

Single gas permeation tests with N₂ and CO₂ revealed comparable N₂ and CO₂ permeances. On the other hand, CO₂/N₂ gas separation tests performed at different total feed pressures and feed compositions lead to CO₂/N₂ permselectivities as high as 26.0, with the corresponding CO₂ permeance of 6 × 10^?8 mol/m² Pa s. The effects of changing the partial pressure gradient of CO₂ across the membrane by means of varying the total feed pressure and the feed composition on the CO₂ permeance and CO₂/N₂ permselectivity are discussed.     

Hydrotalcites for adsorption of CO2 at high temperature

Adsorption of carbon dioxide by hydrotalcites was investigated by using a gravimetric method at 450 ‡C. Hydrotalcites possessed higher adsorption capacity of CO₂ than other basic materials such as MgO and Al₂O₃. Two different preparation methods of hydrotalcite with varying Mg/Al ratio were employed to determine their effects on the adsorption capacity of CO₂. In addition, varying amounts of K₂CO₃ were impregnated on the hydrotalcite to further increase its adsorption capacity of CO₂. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 showed the most favorable adsorption-desorption pattern with high adsorption capacity of CO₂. K₂CO₃ impregnation on the hydrotalcite increased the adsorption capacity of CO₂ because it changed both the chemical and the physical properties of the hydrotalcite. The optimum amount of K₂CO₃ impregnation was 20 wt%. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 and 20 wt% K₂CO₃ impregnation has the highest adsorption capacity of CO₂ with 0.77 mmol CO₂/g at 450 ‡C and 800 mmHg.     

Study of transport of pure and mixed CO2/N2 gases through polymeric membranes

The permeations of pure CO₂ and N₂ gases and a binary gas mixture of CO₂/N₂ (20/80) through poly(dimethylsiloxane) (PDMS) membrane were carried out by the new permeation apparatus. The permeation and separation behaviors were characterized in terms of transport parameters, namely, permeability, diffusion, and solubility coefficients which were precisely determined by the continuous‐flow technique. In the permeation of the pure gases, feed pressure and temperature affected the solubility coefficients of CO₂ and N₂ in opposite ways, respectively; increasing feed pressure positively affects CO₂ solubility coefficient and negatively affects N₂ solubility coefficient, whereas increasing temperature favors only N₂ sorption. In the permeation of the mixed gas, mass transport was observed to be affected mainly by the coupling in sorption, and the coupling was analyzed by a newly defined parameter permeation ratio. The coupling effects have been investigated on the permeation and separation behaviors in the permeation of the mixed gas varying temperature and feed pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 179–189, 2000     

CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films

Plasticization phenomena can significantly reduce the performance of polymeric membranes in high-pressure applications. Polyetherimides (PEIs) are a promising group of membrane materials that combine relatively high CO₂/CH₄ selectivities with high chemical and thermal stability. In this work sorption, swelling, and mixed gas separation performance of 3,3′,4,4′-oxydiphthalic dianhydride (ODPA)-based PEI polymers, with 1, 2 or 3 para-aryloxy substitutions in the diamine moeiety, is investigated under conditions where commercial membranes suffer from plasticization. Particular focus is on the influence of the amount of para-aryloxy substitutions and the film thickness. Results are compared with those of commercially available polymeric membrane materials (sulphonated PEEK, a segmented block-co-polymer PEBAX and the polyimide Matrimid).The glassy polymers display increasing CO₂ sorption with increasing T_g. The larger extent of sorption results from a larger non-equilibrium excess free volume. Swelling of the polymers is induced by sorption of CO₂ molecules in the non-equilibrium free volume as well as from molecules dissolved in the matrix. Dilation of the polymer is similar for each molecule sorbed. Correspondingly, the partial molar volume of CO₂ is similar for molecules present in both regions.Mixed gas separation experiments with a 50/50% CO₂/CH₄ feed gas mixture showed high CO₂/CH₄ selectivities for the ODPA PEI films at elevated pressure. This shows that these materials could potentially be interesting for high-pressure gas separation applications, although additional gas permeation experiments using different feed gas compositions and thin films are required.     

Sorption and transport of gases in miscible poly(methyl acrylate)/poly(epichlorohydrin) blends

The sorption and the transport of He, Ar, N₂, CH₄, and CO₂ in miscible poly(methyl acrylate)(PMA)/poly(epichlorohydrin)(PECH) blends from 1 to 20 atm at 35°C are reported. For He, Ar, N₂, and CH₄, the permeabilities and the diffusion time lags are independent of the upstream pressure, if the compaction effect resulting from compression of the polymer membrane onto the supporting medium is eliminated. The permeability of CO₂ increases with upstream pressure but solubility follows a simple Henry's law behavior. For all five gases, the dependence of solubility, diffusion coefficient, and permeability on blend composition are compared with theoretical mixing rules with the conclusion that both the interaction energy density and the excess activation energy for gas diffusion in the blends are near zero. The fact that the specific volumes of the blends exactly follow linear additivity also confirms that only very weak interactions exist between PMA and PECH.     

Separation of CO2 by 2-amino-2-methyl-1-propanol aqueous solution in microporous hydrophobie hollow fiber contained liquid membrane

The absorption of CO₂ from a mixture of CO₂/N₂ gas was carried out using a flat-stirred vessel and the polytetrafluoroethylene hollow fiber contained aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The reaction of CO₂ with AMP was confirmed to be a second order reversible reaction with fast-reaction region. The mass transfer resistance in the membrane side obtained from the comparison of the measured absorption rates of CO₂ in a hollow fiber contained liquid membrane with a flat-stirred vessel corresponded to about 90% of overall-mass-transfer resistance. The mass transfer coefficient of hollow fiber phase could be evaluated, which was independent of CO₂ loading.     

Experimental study of CO2 absorption/stripping via PVDF hollow fiber membrane contactor

Gas–liquid hollow fiber membrane contactor can be a promising alternative for the CO₂ absorption/stripping due to the advantages over traditional contacting devices. In this study, the structurally developed hydrophobic polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared via a wet spinning method. The membranes were characterized in terms of morphology, permeability, wetting resistance, overall porosity and mass transfer resistance. From the morphology analysis, the membranes demonstrated a thin outer finger-like layer with ultra thin skin and a thick inner sponge-like layer without skin. The characterization results indicated that the membranes possess a mean pore size of 9.6 nm with high permeability and wetting resistance and low mass transfer resistance (1.2 × 10⁴ s/m). Physical CO₂ absorption/stripping were conducted through the fabricated gas–liquid membrane contactor modules, where distilled water was used as the liquid absorbent. The liquid phase resistance was dominant due to significant change in the absorption/stripping flux with the liquid velocity. The CO₂ absorption flux was approximately 10 times higher than the CO₂ stripping flux at the same operating condition due to high solubility of CO₂ in water as confirmed with the effect of liquid phase pressure and temperature on the absorption/stripping flux.     

Concentration dependence of diffusivities of penetrants in glassy polymer membranes

Steady-state permeation rates for pure CO₂, CH₄, and O₂ through two kinds of homogeneous dense membranes, copolymer of methyl methacrylate and n-butyl acrylate and poly(methyl methacrylate), were measured at three temperatures between 20 and 40°C and upstream pressures up to 3 MPa. The logarithms of the mean permeability coefficients for CO₂ in both membranes increased linearly or quadratically with increasing upstream pressure, whereas the mean permeabilities for CH₄ and CO₂ were independent of pressure. The pressure dependence of the mean permeability coefficient for CO₂ was interpreted in terms of a modified free-volume model of diffusion for a Henry's law population in glassy polymers. © 1993 John Wiley & Sons, Inc.     

Reaction between CO2 and CaO under dry grinding

This study was carried out to investigate the reaction between CO₂ and materials that contain CaO under dry grinding. Chemical reagent CaO was used in this experiment, and waste concrete was also tested to examine the feasibility of CO₂ sorption into it. Samples were ground in a CO₂ atmosphere by a centrifugal ball mill. The reaction was measured with the constant volume method. The effects of amount of sample, the number and diameter of balls, the concentration of CO₂ in the mixture of CO₂ and air and the rotational speed on the CO₂ sorption were examined. The amount of the CO₂ sorption under grinding was larger than that without grinding. The grinding enhanced the reaction between CaO and CO₂. The CO₂ sorption steeply increased with time in the early stage of grinding. After that, it increased gradually. The CO₂ reacted with the CaO at the surface layer of the newly exposed surface of the CaO particles during the grinding. The initial sorption rate of CO₂ was related with the shear force. In the latter stage of grinding, the grinding process caused the CaO particles to agglomerate. As a result, the sorption of CO₂ became slow. It was found that the waste concrete had high potential for sorption of CO₂ by means of dry grinding.     

Gas permeability of NH3‐plasma‐treated poly(methyl methacrylate) membranes

The effect of NH₃ plasma treatment on glassy poly(methyl methacrylate) (PMMA) membranes on the diffusion process for penetrant gases (CO₂, O₂, and N₂) was investigated from mean permeability data. The mean permeability coefficient for CO₂ definitely depended on the upstream pressure, whereas those for O₂ and N₂ remained constant regardless of the upstream pressure. For O₂ transport, the permeability increased a little with increasing treatment power, and for N₂ transport, it was not affected by the treatment power. For CO₂ transport, NH₃ plasma treatment promoted the transport of Langmuir mode, presumably through an increased Langmuir capacity constant for CO₂. NH₃ plasma treatment for PMMA membranes resulted in an increase in the separation factor of CO₂ relative to N₂ and in the permeability to CO₂. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1068–1072, 2003     

Infrared spectroscopic study and characteristics of SnO2-based thick film for CH3CN detection

The SnO₂/Al₂O₃/Nb₂O₅/ISiO₂ thick film devices were fabricated by screen printing and dipping methods, and their sensing characteristics to CH₃CN gas was investigated. The oxidation products of CH₃CN on the thick film were analyzed by FT-IR using a heatable gas cell. The IR results showed that the products formed by oxidation of CH₃CN at 300 ‡C on the SnO₂/Al₂/Nb₂O₅ thick film without SiO₂ were mainly CO₂, H₂O, and NH₃, while on the SnO₂/Al₂O₃/Nb₂O₅/SiO₂ thick film products such as CO₂, H₂O, N₂O, HNO₃, and HNO₂ were observed. The thick film devices containing SiO₂ showed high selectivity and negative sensitivity to CH₃CN due to the presence of nitrogen compounds produced by oxidation of CH₃CN. Optimum amount of Nb₂O₅ and operating temperature were 1. 0 wt% and 300 ‡C, respectively.     

Effect of temperature on reduction reactivity of oxygen carrier particles in a fixed bed chemical-looping combustor

In a chemical-looping combustor (CLC), gaseous fuel is oxidized by metal oxide particle, e.g. oxygen carrier, in a reduction reactor (combustor), and the greenhouse gas CO₂ is separated from the exhaust gases during the combustion. In this study, NiO/bentonite particle was examined on the basis of reduction reactivity, carbon deposition during reduction, and NO_x formation during oxidation. Reactivity data for NiO/bentonite particle with methane and air were presented and discussed. During the reduction period, most of the CH₄ are converted to CO₂ with small formation of CO. Reduction reactivity (duration of reduction) of the NiO/bentonite particle increased with temperature, but at higher temperature, it is somewhat decreased. The NiO/bentonite particle tested showed no agglomeration or breakage up to 900 ‡C, but at 1,000 ‡C, sintering took place and lumps of particles were formed. Solid carbon was deposited on the oxygen carrier during high conversion region of reduction, i.e., during the end of reduction. It was found that the appropriate temperature for the NiO/bentonite particle is 900 ‡C for carbon deposition, reaction rate, and duration of reduction. We observed experimentally that NO, NO₂, and N₂O gases are not generated during oxidation.     

Real time intracellular pH dynamics in Listeria innocua under CO2 and N2O pressure

This article investigates the inactivation mechanism of high-pressure food treatment, considered as alternative to conventional biocidal processes. We aimed to determine intracellular pH decrease under CO₂ and N₂O pressure, so far postulated as one of the main causes of inactivation. Working with a lab-scale bioreactor in mild conditions – 25 °C and pressures up to 8 MPa – we monitored – for the first time during pressurization – cytoplasmic pH variations of Listeria innocua labeled with pH-sensitive fluorophores based on fluorescein.We show that carbonic acid, due to solubilization of CO₂ into the aqueous phase, causes a rapid pH drop in the cytosol, reaching pH 4.8 at 1 MPa and falls below the detection limit of the indicator fluorophore of pH 4.0. This correlates with a reduced viability (below 90%) in all the pressure ranges investigated. Contrarily, treatment under N₂O pressure reduces cell viability without significant pH-drop neither of intra- nor extra-cellular liquid at any pressure investigated. The pH value remains between 7 and 6 while an inactivation of more than 80% is achieved at 8 MPa.Our data clearly demonstrate that, as a critical pressure is achieved, microbial inactivation is mainly due to pressure-induced membrane permeation – stimulated by non-acidifying fluids as well, rather then cytoplasmic acidification, as widely argued so far. A definitive understanding of the microbial inactivation mechanism due to CO₂/N₂O under pressure has been advanced significantly.     

Modification of polycarbonate membrane by polyethylene glycol for CO2/CH4 separation

In this study, permeation of carbon dioxide (CO₂) and methane (CH₄) through the polycarbonate/polyethylene glycol (PC/PEG) blend membrane was investigated. The effect of PEG content (0–5 wt%) on the permeability and selectivity was studied. Permeability measurements were carried out at pressures of 1–7 bar and at room temperature. The membranes were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and density measurement. The results revealed that the PC/PEG blends are miscible/partially miscible without considerable micro-phase separation. The effect of PEG content and gas pressure on the diffusion and solubility of coefficients were also investigated and analyzed. It was concluded that the most influential parameter for the permeation is the diffusion coefficient of the gases. The permeability and selectivity decrease as the operating pressure and PEG content are increased. Furthermore, the results showed that the addition of 5 wt% of PEG into PC increases the CO₂/CH₄ selectivity from 26.6 ± 0.99 to 40.9 ± 2.14 (more than 53%) at 1 bar.     

Gas absorption of carbon dioxide in a hollow fiber contained liquid membrane absorber

Experiments on the absorption of CO₂ into a hollow fiber contained liquid membrane absorber were performed. The feed gas was a mixture of CO₂ and N₂, absorbent liquid was 2-amino-2-methyl-l-propanol and the hollow fiber was a microporous hydrophobic polytetrafluoroethylene membrane. Outlet concentration of CO₂ from the absorber decreased as absorbent concentration increased, gas flow rate increased and were held constant for speed of agitation, but had a maximum value in the range of inlet concentration of CO₂ from 5 to 40 mole%. The reaction rate constant obtained for CO₂-amine system was 231 I/mol · s at 25 °C using a flat stirred vessel, and the membrane-side-mass-transfer coefficient was 1.217 × 10⁻⁵ mol/cm² · s · atm in CO2/N2-amine system. A diffusion model based on mass transfer with fast-reaction was proposed to predict the performance of the absorber.     

Polyurethane/polyethersulfone dual-layer anisotropic membranes for CO2 removal from flue gas

Removing CO₂ from flue gas streams has been a permanent challenge regarding environmental issues. Membrane technology is a solution for this problem but more efficient membranes are required. The fabrication of dual-layer polyurethane/polyethersulfone membrane by the co-casting technique is undertaken and the effects of previous evaporation time and coagulation water bath temperature on membrane morphology are explored. Uniform layers with excellent adhesion are obtained. The effect of feed pressure and temperature on membrane permeability and selectivity for CO₂, N₂, and O₂ are studied. Increasing the pressure from 1 to 8 bar results in a reduction of CO₂ permeability and CO₂/N₂ ideal selectivity from 19.6 to 13.0 barrer, and from 66 to 60, respectively. Temperature in the range of 25–45°C enhances CO₂ permeability from 19.6 to 28.9 barrer, although CO₂/N₂ selectivity decreases from 66 to 43, yet showing good potential for applications.