A high CO2 permselective mesoporous silica/carbon composite membrane for CO2 separation

Ordered mesoporous silica/carbon composite membranes with a high CO₂ permeability and selectivity were designed and prepared by incorporating SBA-15 or MCM-48 particles into polymeric precursors followed by heat treatment. The as-made composite membranes were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and N₂ adsorption, of which the gas separation performance in terms of gas permeability and selectivity were evaluated using the single gas (CO₂, N₂, CH₄) and gas mixtures (CO₂/N₂ and CO₂/CH₄, 50/50 mol.%). In comparison to the pure carbon membranes and microporous zeolite/C composite membranes, the as-made mesoporous silica/C composite membranes, and the MCM-48/C composite membrane in particular, exhibit an outstanding CO₂ gas permeability and selectivity for the separation of CO₂/CH₄ and CO₂/N₂ gas pairs owing to the smaller gas diffusive resistance through the membrane and additional gas permeation channels created by the incorporation of mesoporous silicas in carbon membrane matrix. The channel shape and dimension of mesoporous silicas are key parameters for governing the gas permeability of the as-made composite membranes. The gas separation mechanism and the functions of porous materials incorporated inside the composite membranes are addressed.     

Matrimid‐based carbon tubular membranes: The effect of the polymer composition

In this article, we present a development study of new membrane materials and enhancements of productive membranes to improve the current performance of polymeric membranes. Carbon membranes are a promising material for this matter as they offer an improvement in the gas‐separation performance and exhibit a good combination of permeability and selectivity. Carbon membranes produced from the carbonization of polymeric materials have been reported to be effective for gas separation because of their ability to separate gases with almost similar molecular sizes. In this study, a carbon support membrane was prepared with Matrimid 5218 as a polymeric precursor. The polymer solution was coated on the surface of a tubular support with the dip‐coating method. The polymer tubular membrane was then carbonized under a nitrogen atmosphere with different polymer compositions of 5–18 wt %. The carbonization process was performed at 850°C at a heating rate of 2°C/min. Matrimid‐based carbon tubular membranes were fabricated and characterized in terms of their structural morphology, thermal stability, and gas‐permeation properties with scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and a pure‐gas‐permeation system, respectively. Pure‐gas‐permeation tests were performed with the pure gases carbon dioxide (CO₂) and N₂ at room temperature at a pressure of 8 bar. On the basis of the results, the highest CO₂/N₂ selectivity of 75.73 was obtained for the carbon membrane prepared with a 15 wt % polymer composition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42394.     

Quest for high performance carbon capture membranes: Fabrication of SAPO-34 and CNTs-doped polyethersulfone-based mixed-matrix membranes

Gas separation process is an effective method for capturing and removing CO₂ from post-combustion flue gases. Due to their various essential properties such as ability to improve process efficiency, polymeric membranes are known to dominate the market. Trade-off between gas permeability and selectivity through membranes limits their separation performance. In this study, solution casting cum phase separation method was utilized to create polyethersulfone-based composite membranes doped with carbon nanotubes (CNTs) and silico aluminophosphate (SAPO-34) as nanofiller materials. Membrane properties were then examined by performing gas permeation test, chemical structural analysis and optical microscopy. While enhancing membranes CO₂ permeance, SAPO-34 and CNTs mixture improved their CO₂/N₂ selectivity. By carefully adjusting membrane casting factors such as filler loadings. Using Taguchi statistical analysis, their carbon capture efficiency was improved. The improved mixed-matrix membrane with loading of 5 wt% CNTs and 10 wt% SAPO-34 in PES showed highly promising separation performance with a CO₂ permeability of 319 Barrer and an ideal CO₂/N₂ selectivity of 12, both of which are within the 2008 Robeson upper bound. A better mixed-matrix membrane with outstanding CO₂/N₂ selectivity and CO₂ permeability was produced as a result of the synergistic effect of adding two types of fillers in optimized loading.     

Adsorption and separation of CO2/N2 and CO2/CH4 by 13X zeolite

Accumulation of greenhouse gases in the atmosphere is responsible for increased global warming of our planet. The increasing concentration of carbon dioxide mainly from flue gas, automobile and landfill gas (LFG) emissions are major contributors to this problem. In this work, CO₂, CH₄ and N₂ adsorption was studied on Ceca 13X zeolite by determining pure and binary mixture isotherms using a constant volume method and a concentration pulse chromatographic technique at 40 and 100°C. The experimental data were then compared to the predicted binary behaviour by extended Langmuir model. Results showed that the extended Langmuir theoretical adsorption model can only be applied as an approximation to predict the experimental binary behaviour for the systems studied. Equilibrium phase diagrams were obtained from the experimental binary isotherms. For these systems, the integral thermodynamic consistency tests were also conducted. It was found that Ceca 13X exhibits large CO₂/CH₄ and CO₂/N₂ selectivity and could find application in landfill gas purification, CO₂ removal from natural gas and CO₂ removal from ambient air or flue gas streams. © 2011 Canadian Society for Chemical Engineering     

Knudsen diffusion through ZIF-8 membranes synthesized by secondary seeded growth

Herein we demonstrate the synthesis of ZIF-8 membranes via secondary seeded growth on tubular stainless steel porous supports. The membranes were characterized and evaluated for the separation of CO₂/N₂ and N₂/CH₄ gas mixtures. The adsorbate polarizability correlated with the adsorption capacity on ZIF-8, and the amounts of gases adsorbed were in the order: CO₂ > CH₄ > N₂. The CO₂/N₂ separation selectivity’s for the ZIF-8 membranes were close to the Knudsen selectivity, suggesting that Knudsen diffusion through non-ZIF pores dominated the separation. On the other hand, the separation selectivity’s for N₂/CH₄ were slightly higher than the Knudsen selectivity, indicating that the flow contribution from the ZIF pores favored the transport of N₂ over CH₄.     

Fabrication and modification of cellulose acetate based mixed matrix membrane: Gas separation and physical properties

[Cellulose acetate (CA)-blend-multi walled carbon nano tubes (MWCNTs)] mixed matrix membranes (MMMs), [CA/polyethylene glycol (PEG)/MWCNTs] and [CA/styrene butadiene rubber (SBR)/MWCNTs] blend MMMs were prepared by solution casting method for gas separation applications using Tetrahydrofuran (THF) as solvent. Both raw-MWCNTs (R-MWCNTs) and functionalized carboxylic-MWCNTs (C-MWCNTs) were used in membrane preparation. The MWCNTs loading ratio and pressure effects on the gas separation performance of prepared membranes were investigated for pure He, N₂, CH₄ and CO₂ gases. Results indicated that utilizing C-MWCNT instead of R-MWCNTs in membrane fabrication has better performance and (CO₂/CH₄) and (CO₂/N₂) selectivity reached to 21.81 and 13.74 from 13.41 and 9.33 at 0.65 wt% of MWCNTs loading respectively. The effects of PEG and SBR on the gas transport performance and mechanical properties were also investigated. The highest CO₂/CH₄ selectivity at 2 bar pressure was reached to 53.98 for [CA/PEG/C-MWCNT] and 43.91 for [CA/SBR/C-MWCNT] blend MMMs at 0.5 wt% and 2 wt% MWCNTs loading ratio respectively. Moreover, increase of feed pressure led to membrane gas permeability and gas pair selectivity improvement for almost all prepared membranes. The mechanical properties analysis exhibited tensile modules improvement with increasing MWCNTs loading ratio and utilizing polymer blending.     

Transport and stability enhancement in interfacially and dimensionally constrained CO2 selective polymers embedded in nanoporous sieve membranes

Nanocomposite polymer and ultrathin film membranes have shown great promise in enhancing gas permeation and selectivity properties by interfacially straining polymer matrices, yielding structures of higher free volume. However, undesired particle aggregation and short temporal stability remain a big challenge. In the present study, an “inverse” architecture to conventional polymer nanocomposites was investigated, in which the polymer phase poly(l-trimethylsilyl-1-propyne) (PTMSP) was interfacially and dimensionally constrained in nanoporous anodic aluminum oxide (AAO) membranes. While with this architecture the benefits of nanocomposite and ultrathin film membranes could be reproduced and improved upon, also the temporal stability could be enhanced substantially. Gas permeabilities of helium, nitrogen and carbon dioxide were increased over five-fold, and selectivities of CO₂/He and CO₂/N₂ could be enhanced by 40% compared to the pristine bulk phase, while physical aging, caused by free-volume collapse, was reduced twenty-fold compared to ultrathin membranes.     

Highly Perm-Selective Micro-Porous Hydrotalcite-Silica Membrane for Improved Carbon Dioxide-Methane Separation

A notable improvement of carbon dioxide (CO₂) adsorption in meso- and micro-porous membranes was observed when hydrotalcite (HT) was incorporated in the membranes. For carbon dioxide in carbon dioxide-methane (CH₄) mixture, HT-silica membrane successfully overcame the upper permeability/selectivity limitation for glassy and polymeric membranes, despite the absence of a solution-diffusion mechanism that is typically present in the glassy and polymeric membranes. The performance of HT-silica membrane was observed to exceed that of micro-porous silica and high performance zeolitic imidazolate framework (ZIF) membranes. Incorporating unnecessarily high HT content in silica membrane, however, caused the membrane to lose its molecular sieving capacity and resulted in reduced selectivity of the gas.     

Adsorption and separation of CH4/CO2/N2/H2/CO mixtures in hexagonally ordered carbon nanopipes CMK-5

Adsorption and separation of N₂, CH₄, CO₂, H₂ and CO mixtures in CMK-5 material at room temperature have been extensively investigated by a hybrid method of grand canonical Monte Carlo (GCMC) simulation and adsorption theory. The GCMC simulations show that the excess uptakes of pure CH₄ and CO₂ at 6.0 MPa and 298 K can reach 13.18 and 37.56 mmol/g, respectively. The dual-site Langmuir–Freundlich (DSLF) model was also utilized to fit the absolute adsorption isotherms of pure gases from molecular simulations. By using the fitted DSLF model parameters and ideal adsorption solution theory (IAST), we further predicted the adsorption separation of N₂–CH₄, CH₄–CO₂, N₂–CO₂, H₂–CO, H₂–CH₄ and H₂–CO₂ binary mixtures. The effect of the bulk gas composition on the selectivity of these gases is also studied. To improve the storage and separation performance, we finally tailor the structural parameters of CMK-5 material by using the hybrid method. It is found that the uptakes of pure gases, especially for CO_2, can be enhanced with the increase of pore diameter D_i, while the separation efficiency is apparently favored in the CMK-5 material with a smaller D_i. The selectivity at D_i=3.0 nm and 6.0 MPa gives the greatest value of 8.91, 7.28 and 27.52 for S_CO2/N2, S_CH4/H2 and S_CO2/H2, respectively. Our study shows that CMK-5 material is not only a promising candidate for gas storage, but also suitable for gas separation.     

Preparation and Characterization of Polycarbonate-Blend-Raw/Functionalized Multi-Walled Carbon Nano Tubes Mixed Matrix Membrane for CO2 Separation

Membrane composed of PC as base of polymer matrix with different ratio of multiwall carbon nano tubes (MWCNTs) as nanofillers and poly ethylene glycol (PEG) as second polymer was prepared by solution casting method. Both raw-MWCNTs (R-MWCNTs) and functionalized carboxyle-MWCNTs (C-MWCNTs) were used in membrane preparation. The MWCNTs loading ratio and pressure effects on the gas transport properties of membranes were examined in relation to pure He, N₂, CH₄, and CO₂ gases. Results showed that the use of C-MWCNT instead of R-MWCNTs in mixed matrix membranes (MMMs) fabrication with base of PC provides better performance and also it increases (CO₂/CH₄) and (CO₂/N₂) selectivities to 27.38 and 25.42 from 25.45 and 19.24, respectively (at 5 wt% of MWCNTs). PEG as the second rubbery polymer was utilized to improve the separation performance and mechanical properties. In blend MMMs, highest (CO₂/CH₄) selectivity at 2 bar pressure increased to 35.64 for PC/PEG/C-MWCNT blend MMMs which was 27.28 for PC/MWCNTs MMMs at 10 wt%. Increase of feed pressure led to gas permeability and gas pair selectivity improvement in approximately all of membranes. Analysis of mechanical properties showed improvement in tensile modules with the increase of MWCNTs loading ratio and use of PEG in prepared MMMs.     

Pure and mixed gas permeation study of silica incorporated polyurethane-urea membrane modified by MOCA chain extender

Polyurethane-urea (PUU) nanocomposite membranes have been prepared using various loadings of silica (SiO₂) nanoparticles. A Novel PU was fabricated by a two-step bulk polymerization technique based on polycaprolactone (PCL), hexamethylene diisocyanate (HDI), and diamine chain extender, 4,4-methylenebis(2-chloroaniline) (MOCA). The FTIR spectra indicated that the extent of phase separation reduces with increasing SiO₂ content. The presence of crystal regions in the soft and hard segments was confirmed by DSC and XRD analyses. The obtained results illustrated a decrement in the gases' permeation in the presence of SiO₂ particles. By increasing the filler content up to 15 wt% and pressure of 8 bar, the gas permeation value of the CO₂, O₂, and N₂ decreased 36%, 54%, and 59%, respectively. However, the permselectivity of the CO₂/N₂ and O₂/N₂ increased considerably, 55% and 13% respectively. On the contrary, by raising the temperature, a dramatic augmentation in the permeability of all gases with a simultaneous reduction in the selectivity values of both gas pairs was revealed. Increasing the pressure led to a decrease in the permeability values of all membranes for O₂ and N₂, whereas the permeability for CO₂ increased with the pressure. Nevertheless, the selectivity values for the pair of gases increased (at a pressure of 10 bar, 1.66 and 1.17 times the neat PU for CO₂/N₂ and O₂/N₂, respectively). Furthermore, the permeability of the CO₂, O₂, and N₂ for the mixed gases was smaller than for pure ones at the same gas upstream pressure. Nonetheless, like the pure gas, the selectivity of both pair gases increased.     

Improving CO2/CH4 adsorptive selectivity of carbon nanotubes by functionalization with nitrogen-containing groups

Multi-walled carbon nanotubes containing oxygenated groups (O-MWCNTs) have been functionalized with ammonia to improve the adsorption capacity and selectivity of CO₂/CH₄ in gas adsorption process. The effects of oxygen and nitrogen containing functional groups (e.g. hydroxyl and amine), on CO₂ and CH₄ adsorption were studied. The ideal adsorption capacities of MWCNTs were determined using volumetric method at ambient temperature and moderate pressures (from 0.1 to 3.0 MPa). The MWCNTs containing nitrogen groups (N-MWCNTs) showed much higher adsorption capacity of CO₂ and selectivity of CO₂/CH₄ against the O-MWCNTs at different pressures. The highest selectivity was observed at lower pressures at 298 K for the N-MWCNTs. The dynamic adsorption experiments were carried out with a feed containing one to fivefold of CO₂ to CH₄ in a packed bed of N-MWCNTs at 298 K and atmospheric pressure. The breakthrough curves and breakthrough times of CO₂ and CH₄ were determined for the mixed gases. The results indicated high efficiency of the prepared N-MWCNTs in dynamic separation of CO₂ and CH₄.     

Modeling the selectivity of activated carbons for efficient separation of hydrogen and carbon dioxide

Grand canonical Monte Carlo simulations (GCMC) are carried out to investigate the separation of hydrogen and carbon dioxide via adsorption in activated carbons. In the simulations, both hydrogen and carbon dioxide molecules are modeled as Lennard-Jones spheres, and the activated carbons are represented by a slit-pore model. At elevated temperatures (T = 505 and 923 K), the activated carbons exhibit essentially no preference over the two gases and the selectivity of carbon dioxide relative to hydrogen falls monotonically as the pore size increases. At room temperature, however, the selectivity of carbon dioxide relative to hydrogen reaches up to 90, indicating that hydrogen and carbon dioxide can be efficiently separated. Furthermore, the optimized pore sizes, of width H = 1.48 nm for the bulk mole fraction ratio of x_CO2/x_H2=1:2 and H = 1.18 nm for x_CO2/x_H2=1:8, are identified in which the activated carbons show the highest selectivity for the separation of hydrogen and carbon dioxide.     

Structural and transport properties of polydimethylsiloxane based polyurethane/silica particles mixed matrix membranes for gas separation

Mixed matrix membranes of synthesized polyurethane (PU) based on toluene diisocyanate (TDI), polydimethylsiloxane (PDMS) and polytetramethylene glycol (PTMG) with polyvinyl alcohol based polar silica particles were prepared by solution casting technique. The homogeneity and thermal properties of the prepared PDMS-PU/silica membranes were characterized using scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The SEM micrographs confirmed the distribution of silica particles in the polymer matrix without agglomerations. Gas permeation properties of membranes with different silica contents were studied for pure CO₂, CH₄, O₂, He and N₂ gases. The obtained results indicated the permeability of the condensable and polar CO₂ gas was enhanced whereas permeability of other gases decreased upon increasing the silica content of the mixed matrix membranes. The permeability of CO₂ and its selectivity over N₂ was increased from 68.4 Barrer and 22 in pure PDMS-PU to 96.7 Barrer and 64.4 in the mixed matrix membranes containing 10 wt% of the silica particles.     

Poly(ether-b-amide)/Tween20 Gel Membranes for CO2/N2 Separation

Poly(ether-b-amide) (PEBA)/Tween20 gel membranes containing from 0 wt% to 65 wt% of Tween20 in PEBA2533, PEBA3533, and PEBA4033 were prepared by solvent casting method for CO₂/N₂ separation. The gas separation properties of the polymeric gel membranes were tested for single gases of CO₂ and N₂ at 25°C with the feed pressure of 0.6 atm. For all pure PEBA membranes, CO₂ and N₂ permeability decreased as the amount of polyamide block increased, but CO₂/N₂ selectivity increased. For PEBA/Tween20 gel membranes, both the CO₂ permeability and CO₂/N₂ selectivity were greatly enhanced with the increase of Tween20 content. For the membrane of PEBA4033/Tween20-65, CO₂/N₂ selectivity, and CO₂ permeability reached 54 and 146 Barrer, respectively, which is very interesting for potential application in CO₂ removal from flue gas.     

Carbon membranes from cellulose and metal loaded cellulose

The focus of this work was to find a low-cost precursor for carbon molecular sieve (CMS) membranes, and a simple way of producing them. In addition, several ways of modifying a carbon material are described. The modification method used in this study was metal doping of carbon. CMS membranes were formed by vacuum carbonization of cellulose and metal loaded cellulose. Metal additives include oxides of Ca, Mg, Fe(III) and Si, and nitrates of Ag, Cu and Fe(III).The carbon membrane containing Fe-nitrate has promising separation performance for the gas pairs O₂/N₂ and CO₂/CH₄. Carbon containing nitrates of Cu or Ag show high selectivity, but reduced O₂ and CO₂ permeability compared to carbon with Fe-nitrate. Element analysis indicates that Cu migrates to the carbon surface, creating an extra layer resistance to gas transport. A silver mirror is also seen on the surface of Ag-nitrate-containing carbon. However, the Ag- and Cu-containing membranes show a high H₂ permeability. Adding metal oxides makes the carbon membranes retard the transport of easily condensable gases (e.g. CO₂). This can be exploited for enhanced H₂/CO₂ separation efficiency.     

A Novel Adsorption Cycle for CO2 Recovery: Experimental and Theoretical Investigations of a Temperature Swing Compression Process

Abstract

A novel adsorption cycle is examined experimentally and theoretically for recovering carbon dioxide from a 50 mol% mixture with carbon monoxide. Several adsorbents are considered, and zeolite NaY is chosen for the process due to its high capacity and selectivity for CO₂ in the presence of CO. The process consists of three steps. The bed is fed the gas mixture at 273 K until CO₂ breakthrough occurs. The bed then undergoes countercurrent blowdown of CO₂ while heating at 391 K and is finally cooled to the initial feed temperature once the bed has been depleted of CO₂. Results are presented from laboratory scale experiments and are described using numerical simulations. This novel cycle provides a method for capturing and producing CO₂ without the need for a purge gas and has low energy requirements if waste heat is available.     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

Adsorption and Desorption of Carbon Dioxide and Nitrogen on Zeolite 5A

The adsorption equilibrium data of CO₂ and N₂ at (303, 333, 363, 393, 423) K ranging 0-1 bar on zeolite 5A is reported. The pressure and temperature range covers the operating pressure in adsorption units for CO₂ capture from power plants. Experimental data were fitted by the multi-site Langmuir model. The adsorbent is much more selective to CO₂: loading at 303 K and 100 kPa is 3.38 mol/kg while loading of N₂ at the same pressure is 0.22 mol/kg. The Clausius-Clapeyron equation was employed to calculate the isosteric enthalpy of adsorption. The fixed-bed adsorption and desorption of carbon dioxide and nitrogen on zeolite 5A pellets has been studied. A model based on the bi-LDF approximation for the mass transfer, taking into account the energy and momentum balances, had been used to describe the adsorption kinetics of carbon dioxide and nitrogen. The model predicted satisfactorily the breakthrough curves obtained with carbon dioxide–nitrogen mixtures. Desorption process (consisting of depressurization, blowdown, and purge) was also performed. Following the feasibility of concentration and capture of carbon dioxide from flue gases by Pressure Swing Adsorption (PSA) process was simulated. A CO₂ recovery of 91.0% with 53.9% purity was obtained using a five-step Skarstrom-type PSA cycle.     

Solid-state dechlorination pathway for the synthesis of few layered functionalized carbon nanosheets and their greenhouse gas adsorptivity over CO and N2

A simple solid-state dechlorination route has been demonstrated to synthesize few layered functionalized carbon nanosheets (FCNS) utilizing hexachloroethane as carbon source and copper as reducing agent under the autogenic pressure at 300 °C. The obtained FCNS possesses the sheet thickness of 6–12 nm as analyzed by transmission electron microscopy. The particle nature of the FCNS provides the excess porosity having the surface area 836 m²/g. The equilibrium gas adsorption study of FCNS for greenhouse gases (CO₂ and CH₄), toxic gas (CO) and light gas (N₂) showed the maximum adsorption capacity for CO₂ (2.95 mmol/g; at 288 K) with maximum capacity selectivity of 10.1 at 318 K. The very strong adsorbate–adsorbent interaction was observed in case of CO compare to other gases resulted in higher heat of adsorption for CO. The gas adsorption and FT-IR study showed that the interaction of CO with copper present in minute quantities in FCNS improves the CO adsorption due to π complexation. The FCNS obtained under present methodology showed the very high equilibrium selectivity for CO over N₂ (197) followed by CH₄ (61) and CO₂ (7.3) at 288 K.