An in-situ ATR-FTIR Spectroscopy Study of Adsorption in MFI Zeolites A step towards effective upgrading of biofuels

Abstract: Global warming is believed to be caused by the extensive emission of greenhouse gases, for example carbon dioxide, into the atmosphere by combustion of fossil fuels, such as coal, oil and natural gas. To reduce the emission of carbon dioxide and hence avoid global warming, alternative fuels derived from renewable resources are desired. Another reason for the worldwide interest in finding alternative fuels is that the reserves of the fossil fuels are limited and the oil and gas sources will eventually run out. Biogas and biobutanol are renewable biofuels which are interesting alternatives to fossil fuels. Biogas is produced during degradation of organic material forming a mixture of mainly methane and carbon dioxide with water as a common trace component. Biobutanol is produced from ABE (acetone, butanol and ethanol) fermentation of biomass. Purification of biogas and biobutanol is essential to increase the heat value of the fuels. Traditional purification processes are energy demanding and expensive. Therefore, other separation processes are currently sought for. Zeolites are promising alternatives due to their great potential both as selective adsorbents and as membranes. Due to the unique pore structure, zeolites are capable of separating components based on their adsorption properties. In the present work, single component adsorption of biogas components such as methane, carbon dioxide and water in zeolite ZSM-5 was studied as well as adsorption of water and butanol in silicalite-1 using in-situ ATR-FTIR spectroscopy. The method was successfully further used to study multicomponent adsorption. For single gas adsorption experiments, recorded infrared spectra of adsorbed methane, carbon dioxide and water showed characteristic, well separated, bands for each gas. Adsorbed concentrations were determined from the recorded infrared spectra. The Langmuir model was fitted to the adsorption isotherms and the model matched the experimental data very well. The fitted Langmuir parameters obtained in the present work was in agreement with values reported in the literature. For multicomponent adsorption experiments, the Ideal Adsorbed Solution Theory (IAST) was used to predict the adsorbed concentrations of methane, carbon dioxide and water using the single component adsorption isotherm parameters as input. In general, the IAST was shown to be a fairly good model for predicting the adsorbed concentrations of methane and carbon dioxide from binary mixtures. For the amount of adsorbed methane from mixtures including water, the IAST predicted the values fairly well. However, for mixtures containing water and carbon dioxide, the IAST could not fully describe the adsorption behavior of the two components. The CO2/CH4 adsorption selectivity was determined for various gas compositions and temperatures showing a general increase in the selectivity with decreasing temperature. This indicates that the separation of carbon dioxide from biogas should be more efficient at lower temperatures. Compared to the literature,the selectivity observed in the present work is relatively high indicating that Na-ZSM-5 may be an effective membrane material for upgrading biogas. Moreover, butanol was preferentially adsorbed over water in silicalite-1, indicating that silicalite-1 may be a promising material for recovery of butanol from dilute water solutions.