Detailed Investigation of the Binary Adsorption of Carbon Dioxide and Methane in Zeolite Na-ZSM‑5 Studied Using in Situ ATR-FTIR Spectroscopy

The separation of carbon dioxide from methane is an important process when purifying biogas and natural gas. Zeolite membranes and adsorbents are among the technologies suggested for efficient separation of carbon dioxide from these gases. In the present work, the adsorption of carbon dioxide and methane from binary mixtures in a low alumina Na-ZSM-5 zeolite film at various gas compositions and temperatures was studied using in situ ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopy. Adsorbed concentrations were successfully extracted from infrared spectra. The experimental values of the adsorbed phase mole fraction of carbon dioxide and methane were compared to values predicted using the ideal adsorbed solution theory (IAST). The values predicted with the IAST agreed very well with values determined experimentally. The CO₂/CH₄ adsorption selectivity was determined, and at 35 °C a selectivity of 15.4 was obtained for an equimolar gas mixture. At the highest (0.9) and lowest (0.03) investigated mole fractions of carbon dioxide in the gas phase, the selectivity was higher compared to the other investigated mole fractions. At 35 °C the highest observed selectivity values were 31.1 and 20.4 for the highest and the lowest adsorbed mole fraction, respectively. At compositions closest to those found in biogas and natural gas, there was a decrease in the selectivity at higher temperatures, indicating that separation of carbon dioxide from methane in biogas and natural gas may be more efficient at low temperatures

Influence of Zn(II) on the Adsorption of Arsenate onto Ferrihydrite

Addition of iron oxide to arsenic-contaminated soil has been proposed as a means of reducing the mobility of arsenic in the soil. Arsenic and zinc are common coexisting contaminants in soils. The presence of zinc therefore may affect the adsorption properties of arsenic on iron oxide, and may thus affect its mobility in the soil. The influence of Zn­(II) on the adsorption of arsenate ions on iron oxide was studied. Batch adsorption experiments indicated that Zn­(II) increased the arsenate removal from a solution by ferrihydrite at pH 8. However, ATR-FTIR spectroscopy showed that no adsorption of arsenate on a ferrihydrite film occurred at pD 8 in the presence of Zn­(II). Precipitation of zinc hydroxide carbonate followed by arsenate adorption onto the precipitate was found to be a plausible mechanism explaining the arsenate removal from a solution in the presence of Zn­(II) at pH/pD 8. The previously suggested mechanisms attributing the enhanced removal of arsenate from solution in the presence of Zn­(II) to additional adsorption on iron oxides could not be verified under the experimental conditions studied. It was also shown that at pH/pD 4, the presence of Zn­(II) in the system did not significantly affect the adsorption of arsenate on ferrihydrite

Adsorption of CO₂, CH₄, and H₂O in Zeolite ZSM‑5 Studied Using In Situ ATR-FTIR Spectroscopy

Biogas and natural gas are interesting fuels with high H/C ratio. However, these gases frequently contain carbon dioxide and water which lowers the heat value of the gas and may induce corrosion. Therefore, the development of more efficient processes, such as membrane processes and improved adsorbents, for the separation of carbon dioxide and water from biogas and natural gas is of great importance. Zeolite ZSM-5 membranes are promising for this separation which is controlled by the adsorption and diffusion of the different species in the zeolite. Multicomponent adsorption data are therefore required for development of new membrane and adsorption processes. In the present work, the adsorption of water, carbon dioxide, and methane in a Na-ZSM-5 zeolite film at various temperatures was studied by in situ Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy for the first time. Adsorption isotherms were retrieved from the experimental data and the Langmuir model fitted the isotherms very well. Limiting heat of adsorption was determined from the Henrýs law regime and the values determined agreed well with previously reported data. A few experiments were conducted with multicomponent mixtures and the experimentally determined amounts adsorbed were compared with values predicted by the Ideal Adsorbed Solution Theory (IAST). It was found that for the binary mixture of carbon dioxide and methane there was good agreement between the experimental values and those predicted by the IAST. However, when water was also introduced, the IAST could not fully capture the adsorption behavior of the multicomponent mixture, probably because the adsorbed phase is not ideal. These findings are in line with previous reports for adsorption in zeolites. The multicomponent adsorption behavior of this system will be further investigated in forthcoming work

Effect of Water on the Adsorption of Methane and Carbon Dioxide in Zeolite Na-ZSM‑5 Studied Using <i>in Situ</i> ATR-FTIR Spectroscopy

Methane is the main component in biogas and natural gas along with contaminants such as water and carbon dioxide. Separation of methane from these contaminants is therefore an important step in the upgrading process. Zeolite adsorbents and zeolite membranes have great potential to be cost-efficient candidates for upgrading biogas and natural gas, and in both of these applications, knowing the nature of the competitive adsorption is of great importance to further develop the properties of the zeolite materials. The binary adsorption of methane and carbon dioxide in zeolites has been studied to some extent, but the influence of water has been much less studied. In the present work, <i>in situ</i> ATR (attenuated total reflection)–FTIR (Fourier transform infrared) spectroscopy was used to study the adsorption of water/methane and water/carbon dioxide from binary mixtures in a high-silica Na-ZSM-5 zeolite film at various gas compositions and temperatures. Adsorbed concentrations for all species were determined from the recorded IR spectra, and the experimental values were compared to values predicted using the ideal adsorbed solution theory (IAST). At lower temperatures (35, 50, and 85 °C), the IAST was able to predict the binary adsorption of water and methane, whereas the values predicted by the IAST deviated from the experimental data at the highest temperature (120 °C). For the binary adsorption of water and carbon dioxide, the IAST could not predict the adsorption values accurately. This discrepancy was assigned to the particular adsorption behavior of water in high-silica MFI forming clusters at hydrophilic sites. However, the predicted values did follow the same trend as the experimental values. The adsorption selectivity was determined, and it was found that the H₂O/CH₄ adsorption selectivity was decreasing with increasing water content in the gas phase at low temperatures whereas the selectivity was increasing at higher temperatures. The H₂O/CO₂ adsorption selectivity was increasing with increasing water content at all temperatures