Adsorption of water, carbon dioxide and methane in zeolite ZSM-5 studied using in-situ ATR-FTIR spectroscopy

Detta är en avhandling från Luleå tekniska universitet

Sammanfattning: Global warming is believed to be caused by the extensive emission of greenhouse gases, such as 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 fossile fuels are limited and the oil and gas resources will eventually run out. Biogas and natural gas are interesting alternatives with no or at least reduced emission of fossil carbon dioxide to the atmosphere as compared to coal and oil. Both gases mainly consist of methane (60–95%) but may also contain a large fraction of carbon dioxide and water. Removal of carbon dioxide and water from biogas and natural gas is of great importance mainly to lower the transportation costs and to increase the heat value of the gas. The most commonly used separation technique is amine absorption. This is an expensive and complex process and alternative techniques are desired. Zeolites are an interesting alternative due to their great potential both as selective adsorbents and membranes. Due to the unique pore structure zeolites are capable of separating species in a mixture based on the molecule size and adsorption properties. Since water, carbon dioxide and methane all have a molecular size smaller than the pore size of the zeolite ZSM-5 studied in the present work, the molecules can enter and adsorb in the pores and hence the separation is based on adsorption rather than size. In the present work, the single component adsorption of water, carbon dioxide and methane in zeolite ZSM-5 was studied using in-situ Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and the method was successfully further used to study multicomponent adsorption in zeolites. For single gas adsorption experiments, recorded infrared spectra of adsorbed water, carbon dioxide and methaneshowed characteristic well separated bands for each gas. Adsorbed concentrations of water, carbon dioxide and methane were determined from the recorded infrared spectra. For single gas experiments, 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 showed good 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 water, carbon dioxide and methane using the single component adsorption isotherm parameters as input. The IAST accurately predicted the adsorbed concentrations of both carbon dioxide and methane when adsorbed from binary mixtures. Internary mixtures, also including water, the IAST accurately predicted the adsorbed concentration of methane, however it severely underestimated the adsorbed concentration of carbon dioxide.The latter is probably an effect of a non-ideal behavior of carbon dioxide in the presence of water. The CO2/CH4 adsorption selectivity was determined for various gas compositions and temperatures showing a general increase in the selectivity with decreasing temperature, which is related to the higher heat of adsorption of carbon dioxide. This indicates that the separation of carbon dioxide from biogas and natural gas should be more efficient at lower temperatures. Compared to the literature, the selectivity observed in the present work is relatively high indicating that low silica Na-ZSN-5 may be an effective membrane material.

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