High temperature H2/CO2 separation using cobalt oxide silica membranes

In this work high quality cobalt oxide silica membranes were synthesized on alumina supports using a sol–gel, dip coating method. The membranes were subsequently connected into a steel module using a graphite based proprietary sealing method. The sealed membranes were tested for single gas permeance of He, H₂, N₂ and CO₂ at temperatures up to 600 °C and feed pressures up to 600 kPa. Pressure tests confirmed that the sealing system was effective as no gas leaks were observed during testing. A H₂ permeance of 1.9 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ was measured in conjunction with a H₂/CO₂ permselectivity of more than 1500, suggesting that the membranes had a very narrow pore size distribution and an average pore diameter of approximately 3 Å. The high temperature testing demonstrated that the incorporation of cobalt oxide into the silica matrix produced a structure with a higher thermal stability, able to resist thermally induced densification up to at least 600 °C. Furthermore, the membranes were tested for H₂/CO₂ binary feed mixtures between 400 and 600 °C. At these conditions, the reverse of the water gas shift reaction occurred, inadvertently generating CO and water which increased as a function of CO₂ feed concentration. The purity of H₂ in the permeate stream significantly decreased for CO₂ feed concentrations in excess of 50 vol%. However, the gas mixtures (H₂, CO₂, CO and water) had a more profound effect on the H₂ permeate flow rates which significantly decreased, almost exponentially as the CO₂ feed concentration increased.     

BaCe0.85Tb0.05Co0.1O3−δ perovskite hollow fibre membranes for hydrogen/oxygen permeation

Co-doped BaCe_0.85Tb_0.05Co_0.1O_3−δ (BCTCo) nanopowder was synthesized via a sol–gel method using ethylenediaminetetraacetic acid (EDTA) and citric acid as the chelating agents. Using the resultant powder, BCTCo perovskite hollow fibre membranes were then fabricated by the combined phase inversion and sintering technique. Properties of the BCTCo powder and the hollow fibre membranes in terms of crystalline phase, morphology, electrical conductivity, porosity, mechanical strength and hydrogen/oxygen permeation were investigated by a variety of characterization methods. The results indicated that doping of cobalt in the BCTb oxide led to a higher electrical conductivity and lower calcination temperature for the powder precursor to a perovskite structure as well as sintering temperature for the hollow fibre precursors to gastight membranes. In order to obtain gastight and robust hollow fibre membranes, the sintering temperature should be controlled between 1300 and 1450 °C. The maximum hydrogen flux through the BCTCo hollow fibre membranes reached up to 0.385 mL cm⁻² min⁻¹ at 1000 °C under 50% H₂–He/N₂ gradient, which is higher than that of the un-doped BCTb hollow fibre membranes with the same effective thickness, and especially much higher than that obtained from other proton conductors due to the asymmetric structure of the membrane designed. Moreover, the BCTCo hollow fibre membrane also exhibited noticeable oxygen permeation fluxes, i.e. 0.122 mL cm⁻² min⁻¹ at 1000 °C under the air/He gradient. However, doping of cobalt might damage the mechanical stability of the perovskite membranes in the hydrogen-containing atmosphere.     

H2S removal from biogas for fuelling MCFCs: New adsorbing materials

Cu and Zn modified 13X zeolites prepared by ion exchange or impregnation and activated carbons (ACs) treated with KOH, NaOH or Na₂CO₃ solutions were studied as H₂S sorbents for biogas purification for fuelling molten carbonate fuel cells. H₂S sorption was studied in a new experimental set-up equipped with a high sensitivity potentiometric system for the analysis of H₂S. Breakthrough curves were obtained at 40 °C with a fixed bed of 20 mg of the samples under a stream (6 L h⁻¹) of 8 ppm H₂S/He mixture. The adsorption properties of 13X zeolite improved with addition of Cu or Zn:Cu exchanged zeolite showed the best performances with a breakthrough time of 580 min at 0.5 ppm H₂S, that is 12 times longer than the parent zeolite. In general, unmodified and modified ACs were more effective H₂S sorbents than zeolites. Treating ACs with NaOH, KOH, or Na₂CO₃ solutions improved the H₂S adsorption properties: AC treated with Na₂CO₃ was the most effective sorbent, showing a breakthrough time of 1222 min at 0.5 ppm, that is twice the time of the parent AC.     

Promotion of H2 production from ethanol steam reforming by zeolite basicity

The effect of the basicity of zeolite as a metallic catalyst substrate on ethanol steam reforming reaction was investigated. Catalysts with various basicities were prepared using an ion exchange process with aqueous solutions including Na⁺, K⁺ and Cs⁺ after an impregnation process of Ni on Na-Y zeolite (referred to as Ni/Na-Y, Ni/K-Y and Ni/Cs-Y, respectively). Infrared spectroscopy indicated that the OH bonds of ethanol molecules adsorbed on zeolites were weakened with increasing zeolite basicity. H₂ production at 300 °C increased in the order of Ni/Cs-Y > Ni/K-Y > Ni/Na-Y, and selectivity for a high production ratio of H₂ to C₂H₄ was significantly promoted by exchanging Na⁺ for K⁺ or Cs⁺. H₂ production at 500 °C was also enhanced by the zeolite basicity; however, degradation of catalytic activity was mainly caused by carbon deposition on the three samples at this temperature. Ni/Cs-Y, with higher H₂ production than Ni/Na-Y, also exhibited higher resistance to carbon deposition. Increase of the zeolite basicity was effective for selective acceleration of the dehydrogenation reaction with ethanol, inhibition of coke deposition, and the promotion of H₂ production.     

Highly selective high-silica SSZ-13 zeolite membranes for H2 production from syngas

A highly CO₂-selective high-silica SSZ-13 zeolite membrane was used for H₂ production by separating CO₂ from syngas (CO₂/H₂ mixture). High-silica SSZ-13 zeolite membranes were fabricated using outside asymmetric alumina tubes by secondary growth of ball-milled SSZ-13 seeds. The composition of membrane gel and synthesis time were modified. The Si/Al ratio in framework of the membrane was as high as 42 when SiO₂/Al₂O₃ ratio of the gel increased to 140. The effects of test parameters such as pressure drop, temperature, feed flow rate and concentration on membrane performance were investigated. The test pressure drop was up to 2 MPa. The ultra-high CO₂/H₂ selectivity of 161 with excellent CO₂ permeances of ~6.3 × 10⁻⁷ mol/(m² s Pa) (=3760 GPU) were observed for the best membrane at 243 K and pressure drop of 0.2 MPa. Carbon dioxide permeance through high-silica SSZ-13 zeolite membrane was 4.2 × 10⁻⁷ mol/(m² s Pa) (=2500 GPU) at 298 K and pressure drop of 2.0 MPa, and the CO₂/H₂ selectivity was 17.4. The current high-silica SSZ-13 zeolite membranes exceeded the upper bound of polymeric membranes and other inorganic membranes in CO₂/H₂ plots and owned great potentials for H₂ production from syngas.     

Rapid thermal processing of tubular cobalt oxide silica membranes

This work is the first demonstration of rapid thermal processing techniques as applied to metal oxide/silica membranes on tubular geometries. A procedure was developed which combined fast sol–gel synthesis, rapid calcination steps and a thermal annealing stage to reduce the membrane fabrication time by more than two-thirds, from a conventional process taking seven or more days to less than two. A significant aspect of this major development was the use of a pre-hydrolysed silica precursor ethyl silicate 40 (ES40), instead of the generally preferred tetraethyl orthosilicate (TEOS) which eliminated the need for the researcher specific and time consuming sol–gel reaction stages prior to membrane fabrication. As a result, modified-silica membranes containing cobalt oxides could be directly calcined at 600 °C, instead of conventional thermal process which require slow ramping rates of ≤1 °C min⁻¹ to avoid cracking. As-prepared membranes delivered H₂ permeances of 5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 450 °C and H₂/N₂ permselectivities of 54. The RTP techniques demonstrated in this work greatly reduced the production time and should both allow researchers to significantly increase their productivity and ultimately reduce the barriers for deployment of inorganic membranes into industrial applications.     

Application of phosphoric acid and phytic acid-doped bacterial cellulose as novel proton-conducting membranes to PEMFC

Novel proton-conducting polymer electrolyte membranes have been prepared from bacterial cellulose by incorporation of phosphoric acid (H₃PO₄/BC) and phytic acid (PA/BC). H₃PO₄ and PA were doped by immersing the BC membranes directly in the aqueous solution of H₃PO₄ and PA, respectively. Characterizations by FTIR, TG, TS and AC conductivity measurements were carried out on the membrane electrolytes consisting of different H₃PO₄ or PA doping level. The ionic conductivity showed a sensitive variation with the concentration of the acid in the doping solution through the changes in the contents of acid and water in the membranes. Maximum conductivities up to 0.08 S cm⁻¹ at 20 °C and 0.11 S cm⁻¹ at 80 °C were obtained for BC membranes doped from H₃PO₄ concentration of 6.0 mol L⁻¹ and, 0.05 S cm⁻¹ at 20 °C and 0.09 S cm ⁻¹ at 60 °C were obtained for BC membranes doped from PA concentration of 1.6 mol L⁻¹. These types of proton-conducting membranes share not only the good mechanical properties but also the thermal stability. The temperature dependences of the conductivity follows the Arrhenius relationship at a temperature range from 20 to 80 °C and, the apparent activation energies (E_a) for proton conduction were found to be 4.02 kJ mol⁻¹ for H₃PO₄/BC membrane and 11.29 kJ mol⁻¹ for PA/BC membrane, respectively. In particular, the membrane electrode assembly fabricated with H₃PO₄/BC and PA/BC membranes reached the initial power densities of 17.9 mW cm⁻² and 23.0 mW cm⁻², which are much higher than those reported in literature in a real H₂/O₂ fuel cell at 25 °C.     

High-performance Ni–BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) membranes for hydrogen separation

Cermet membranes composited of Ni and doped barium cerate have been widely studied for hydrogen separation; however, their practical application is limited primarily by the relatively low permeation rate and instability of doped barium cerate in H₂O and CO₂ containing gases. Here we report our findings on the development of a thin-film cermet membrane consisting of Ni and BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb), supported on a porous Ni–BZCYYb substrate. High fluxes of 1.12 and 0.49 ml min⁻¹ cm⁻² have been demonstrated at 900 °C and 700 °C, respectively, when hydrogen was used as the feed gas on one side and N₂ as the sweep gas on the other side. Most importantly, the high-performance membrane can be easily fabricated by a cost-effective particle-suspension coating/co-firing process, offering great promise for large scale hydrogen separation applications.     

Preparation of a novel bimodal catalytic membrane reactor and its application to ammonia decomposition for COx-free hydrogen production

A novel bimodal catalytic membrane reactor (BCMR) consisting of a Ru/γ-Al₂O₃/α-Al₂O₃ bimodal catalytic support and a silica separation layer was proposed. The catalytic activity of the support was successfully improved due to enhanced Ru dispersion by the increased specific surface area for the γ-Al₂O₃/α-Al₂O₃ bimodal structure. The silica separation layer was prepared via a sol–gel process, showing a H₂ permeance of 2.6 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹, with H₂/NH₃ and H₂/N₂ permeance ratios of 120 and 180 at 500 °C. The BCMR was applied to NH₃ decomposition for CO_x-free hydrogen production. When the reaction was carried out with a NH₃ feed flow rate of 40 ml min⁻¹ at 450 °C and the reaction pressure was increased from 0.1 to 0.3 MPa, NH₃ conversion decreased from 50.8 to 35.5% without H₂ extraction mainly due to the increased H₂ inhibition effect. With H₂ extraction, however, NH₃ conversion increased from 68.8 to 74.4% due to the enhanced driving force for H₂ permeation through the membrane.     

Catalytic performance of Ni-Pr supported on delaminated clay in the dry reforming of methane

Mineral clay modified with Al, polyvinyl alcohol (PVA) and microwaves was used as a support to obtain a Ni-Pr catalyst. This catalytic system was evaluated in the reforming of methane with CO₂. The experiments were carried out under drastic conditions for 300 min, with a 50/50 CH₄/CO₂ mixture, total flux of 80 mL min⁻¹, without dilution gas (WHSV = 96 Lg⁻¹h⁻¹) and without previous reduction. The effect of the calcination temperature of the materials was studied at 500 °C and 800 °C as well as the effect of Pr (evaluating nominal quantities of 0, 1, 3 and 5%). The calcination temperature of the solid influenced the formation of the NiO species which had an effect on the activity and formation of coke on the material. The Pr had a promoter effect on the activity of the catalysts increasing the conversions of the CH ₄ as well as the CO₂. The formation of coke for the catalysts calcined at 500 °C presented a correlation with the praseodymium content while for those catalysts calcined at 800 °C there was no formation of coke.     

High performance ZIF-8/PBI nano-composite membranes for high temperature hydrogen separation consisting of carbon monoxide and water vapor

Two types of advanced nano-composite materials have been formed by incorporating as-synthesized wet-state zeolitic imidazolate frameworks-8 (ZIF-8) nano-particles into a polybenzimidazole (PBI) polymer. The loadings of ZIF-8 particles in the two membranes (i.e., 30/70 (w/w) ZIF-8/PBI and 60/40 (w/w) ZIF-8/PBI) are 38.2 vol % and 63.6 vol %, respectively. Due to different ZIF-8 loadings, variations in particle dispersion, membrane morphology and gas separation properties are observed. Gas permeation results suggest that intercalation occurs when the ZIF-8 loading reaches 63.6 vol %. The incorporation of ZIF-8 particles significantly enhances both solubility and diffusion coefficients but the enhancement in diffusion coefficient is much greater. Mixed gas tests for H₂/CO₂ separation were conducted from 35 to 230 °C, and both membranes exhibit remarkably high H₂ permeability and H₂/CO₂ selectivity. The 30/70 (w/w) ZIF-8/PBI membrane has an H₂/CO₂ selectivity of 26.3 with an H₂ permeability of 470.5 Barrer, while the 60/40 (w/w) ZIF-8/PBI membrane has an H₂/CO₂ selectivity of 12.3 with an H₂ permeability of 2014.8 Barrer. Mixed gas data show that the presence of CO or water vapor impurity in the feed gas stream does not significantly influence the membrane performance at 230 °C. Thus, the newly developed H₂-selective membranes may have bright prospects for hydrogen purification and CO₂ capture in realistic industrial applications such as syngas processing, integrated gasification combined cycle (IGCC) power plant and hydrogen recovery.     

La0.6Sr0.4Co0.8Ni0.2O3−δ hollow fiber membrane reactor: Integrated oxygen separation – CO2 reforming of methane reaction for hydrogen production

An integrated reactor system which combines oxygen permeable La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ (LSCN) perovskite ceramic hollow fiber membrane with Ni based catalyst has been successfully developed to produce hydrogen through oxy-CO₂ reforming of methane (OCRM). Dense La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ hollow fiber membrane was prepared using phase inversion-sintering method. OCRM reaction was tested from 650 °C to 800 °C with a quartz reactor packed with 0.5 g Ni/Al₂O₃ catalyst around the LSCN hollow fiber membrane. CH₄ and CO₂ were used as reactants and air as the oxygen source was fed through the bore side of the hollow fiber membrane. In order to gauge the effectiveness of this membrane reactor system, air flow was closed at 800 °C and dry reforming of methane (DRM) was tested for comparison. The results show that the oxygen fluxes of LSCN membrane swept by helium are nearly 3 times less than those swept by OCRM reactants. With increasing temperature and oxygen supply, methane conversion in the OCRM reactor reaches 100%, but CO₂ conversion decreases from 87% to 72% due to the competition reaction with POM. CO selectivity is as high as nearly 100% at reaction temperatures of 700 °C–800 °C while H₂ selectivity reaches a maximum of 88% at 700 °C. At 800 °C, when air supply was closed and DRM was conducted for comparison, CO selectivity decreased to 91%, resulting in carbon deposition which was around 4 times more than those obtained under OCRM reaction and H₂/CO ratio decreased from 0.93 to 0.74, showing better carbon resistance and higher H₂ selectivity of the Ni-based catalyst over the integrated oxygen separation-OCRM reaction across the LSCN hollow fiber membrane reactor.     

A mixed electronic and protonic conducting hydrogen separation membrane with asymmetric structure

In this work, highly doped ceria with lanthanum, La_0.5Ce_0.5O_2−δ (LDC), are developed as hydrogen separation membrane material. LDC presents a mixed electronic and protonic conductivity in reducing atmosphere and good stability in moist CO₂ environment. LDC separation membranes with asymmetrical structure are fabricated by a cost-saving co-pressing method, using NiO + LDC + corn starch mixture as substrate and LDC as top membrane layer. Hydrogen permeation properties are systemically studied, including the influence of operating temperature, hydrogen partial pressure in feed stream and water vapor in both sides of the membrane on hydrogen permeating fluxes. Hydrogen permeability increases as the increasing of temperature and hydrogen partial pressure in feed gas. Using 20% H₂/N₂ (with 3% of H₂O) as feed gas and dry high purity argon as sweep gas, an acceptable flux of 2.6 × 10⁻⁸ mol cm⁻² s⁻¹ is achieved at 900 °C. The existing of water in both sides of membrane has significant effect on hydrogen permeation and the corresponding reasons are analyzed and discussed.     

An improvement of the hydrogen permeability of C/Al2O3 membranes by palladium deposition into the pores

The development of compact hydrogen separator based on membrane technology is of key importance for hydrogen energy utilization, and the Pd-modified carbon membranes with enhanced hydrogen permeability were investigated in this work. The C/Al₂O₃ membranes were prepared by coating and carbonization of polyfurfuryl alcohol, then the palladium was introduced through impregnation–precipitation and colloid impregnation methods with a PdCl₂/HCl solution and a Pd(OH)₂ colloid as the palladium resources, and the reduction was carried out with a N₂H₄ solution. The resulting Pd/C/Al₂O₃ membranes were characterized by means of SEM, EDX, XRD, XPS and TEM, and their permeation performances were tested with H₂, CO₂, N₂ and CH₄ at 25 °C. Compared with the colloid impregnation method, the impregnation–precipitation is more effective in deposition of palladium clusters inside of the carbon layer, and this kind of Pd/C/Al₂O₃ membranes exhibits excellent hydrogen permeability and permselectivity. Best hydrogen permeance, 1.9 × 10⁻⁷ mol/m² s Pa, is observed at Pd/C = 0.1 wt/wt, and the corresponding H₂/N₂, H₂/CO₂ and H₂/CH₄ permselectivities are 275, 15 and 317, respectively.     

Co-precipitated Ni-Mg-Al catalysts containing Ce for CO2 reforming of methane

Ni-Ce/Mg-Al catalysts were synthesized by means of the carbonate co-precipitation method and subsequent calcination at 500 °C. XRD, XPS, SEM, H₂-TPR and CO₂-TPD were used in order to describe completely the structural, morphological and surface characteristics of the oxides. Ce and Mg had a synergic effect on the CO₂ adsorption capacity of the solids; therefore the incorporation of Ce has promoted the basicity of oxides and their catalytic activity in CO₂ reforming of methane. However, the use of high loads of Ce, which form surface coatings, notoriously reduce the superficial area of the solid and favors the formation of NiO-free with the consequent negative impact on the selectivity and an increase in the formation of coke. The catalyst with molar ratio of Al/Ce = 24 showed the highest conversion and was stable up to 50 h of reaction at 700 °C and 48 Lg⁻¹ h⁻¹.     

Syngas production at intermediate temperature through H2O and CO2 electrolysis with a Cu-based solid oxide electrolyzer cell

Solid Oxide Electrolyzer Cells (SOECs) are promising energy devices for the production of syngas (H₂/CO) by H₂O and/or CO₂ electrolysis. Here we developed a Cu–Ce_0.9Gd_0.1O_2−δ/Ce_0.8Gd_0.2O_2−δ/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ-Ce_0.8Gd_0.2O_2−δ cell and performed H₂O and CO₂ electrolysis experiments in the intermediate temperature range (600°C–700 °C). As a baseline, the cell was first tested in fuel cell operation mode; the sample shows a maximum power density peak of 104 mW cm⁻² at 700 °C under pure hydrogen and air. H₂O electrolysis testing revealed a steady production of hydrogen with a Faraday's efficiency of 32% at 700 °C at an imposed current density of −78 mA cm⁻². CO production was observed during CO₂ electrolysis but higher cell voltages were required. A lower efficiency of about 4% was obtained at 700 °C at an imposed current density of −660 mA cm⁻². These results confirm that syngas production is feasible by water and carbon dioxide electrolysis but further improvements from both the manufacturing and the electrocatalytic aspects are needed to reach higher yields and efficiencies.     

HCl removal from biogas for feeding MCFCs: Adsorption on microporous materials

Modified 13X zeolites and active carbons were studied for HCl adsorption from biogas employed as fuel of MCFCs. 13X zeolite was modified by addition of Cu or Zn by ion exchange or impregnation: commercial active carbon was modified by impregnation with KOH, NaOH or Na₂CO₃ solutions. The materials were tested for HCl adsorption in a laboratory apparatus designed to the scope. The tests were carried out under flow conditions with a 100 ppm HCl/N₂ mixture at T = 40 °C and atmospheric pressure. Breakthrough curves were obtained from potentiometric analysis of HCl in the stream effluent from the adsorption cell. The zeolites modified by ion exchange were more effective for HCl adsorption than those modified by impregnation. The active carbon modified with Na₂CO₃ solution showed the highest adsorption capacity of 3.3 × 10⁻⁴ mol HCl g⁻¹ at breakthrough concentration of 1 ppm.     

Hydrogen permeation through the Pd-Nb-Pd composite membrane: Surface effects and thermal degradation

The composite membranes based on Group 5 metals are capable of H₂ separation with the high speed and infinite selectivity. The chemical and thermal stability are critical issues for the application of such membranes in the field of hydrogen energy. In order to understand the degradation mechanisms, the H₂ permeation through composite Pd_2μm-Nb_100μm-Pd_2μm membranes was investigated in a very wide pressure range: (10⁻⁵-10⁴) Pa. At higher pressures the surface contaminations only moderately decreased the permeation. However the permeation experiments at lower pressures demonstrated that an orders of magnitude change in the probability of H₂ molecule dissociative sticking is actually hidden behind this relatively moderate effect. The membranes poisoned by the surface contaminations could be recovered by their exposure to O₂ at (300-400) °C. Heating at temperature higher than 500 °C resulted in the irreversible decrease of permeation and in the pronounced change of permeation behavior at the variation of H₂ pressure. An extremely high permeation was observed at lower pressures at the clean surface of Pd coating. That allows developing an effective membrane pump for hydrogen isotopes.     

Modifying perovskite-type oxide catalyst LaNiO3 with Ce for carbon dioxide reforming of methane

Perovskite-type oxide catalysts LaNiO₃ and La_1−xCe_xNiO₃ (x ≤ 0.5) were prepared by the Pechini method and used as catalysts for carbon dioxide reforming of methane to form synthesis gas (H₂ + CO). The gaseous reactants consisted of CO₂ and CH₄ in a molar ratio of 1:1. At a GHSV of 10,000 hr⁻¹, CH₄ conversion over LaNiO₃ catalyst increased from 66% at 600 °C to 94% at 800 °C, while CO₂ conversion increased from 51% to 92%. The achieved selectivities of CO and H₂ were 33% and 57%, respectively, at 600 °C. To prevent the deposition of carbon and the sintering nickel species, some of the Ni in perovskite-type oxide catalyst was substituted by Ce. Ce provided lattice oxygen vacancies, which activated C–H bonds, and increased the selectivity of H₂ to 61% at 600 °C. XRD analysis indicates that the catalyst exhibited a typical perovskite spinel structure and formed La₂O₂CO₃ phases after CO₂ reforming. The FE-SEM results reveal carbon whisker of the LaNiO₃ catalyst and the BET analysis indicates that the specific surface area increases after the reforming reaction. The H₂-TPR results confirm that Ce metals can store and provide oxygen.     

Carbon monoxide, dinitrogen and carbon dioxide adsorption on zeolite H-Beta: IR spectroscopic and thermodynamic studies

Variable temperature IR spectroscopy (VTIR) was used to investigate the adsorption thermodynamics of carbon monoxide, dinitrogen and carbon dioxide on the protonic zeolite H-Beta. Interaction of the adsorbed gases with the zeolite Brønsted acid sites was found to involve an enthalpy change of −27, −19 and −33 kJ mol⁻¹ for CO, N₂ and CO₂, respectively; the corresponding entropy change was −150, −140 and −146 J mol⁻¹ K⁻¹. The adsorbed gases showed also a weak interaction with silanols, which involves a ΔH⁰ value in the approximate range of −7 to −10 kJ mol⁻¹. These results were discussed in the context of gas separation and carbon capture and sequestration (CCS) using zeolites.