Raw natural gas contains acid gases such as H2S and C02 which must be removed before the gas can be sold. The removal of these gases is called "sweetening" and the use of Diethanolamine (DEA) as a solvent has become widely accepted by industry. The process is simply based on the absorption and desorption of the acid gases in aqueous DEA. Side reactions can occur when DEA reacts with the C02 to produce degradation compounds. This degradation causes a loss in valuable DEA and an increase in plant operating costs. The reaction between DEA and C02 was studied experimentally, using a 600 ml stirred autoclave, to determine the effect of temperature, DEA concentration, and reaction pressure. Degraded DEA samples were analysed using gas chromatography. A fast, simple, and reliable technique was developed to analyse degraded DEA samples, which was ideally suited to plant use. Over 12 degradation compounds were detected in the degraded DEA solutions using gas chromatography and mass spectroscopy. Degradation mechanisms are proposed for the production of the various compounds. It was found that the degradation of DEA was very sensitive to temperature, DEA concentration, and C02 solubility of less than 0.2 g C02/g DEA. To study the effect of C02 solubility, which is a function of reaction pressure, simple solubility experiments were performed to cover the range of 100-200°C, 413.7-4137 kPa (60-600 psi) partial pressure of C02 and DEA concentration of 10, 20, and 30 wt % DEA. It was found that the reaction between DEA and C02 was extremely complex consisting of a mixture of equilibria, parallel, series, and ionic reactions. However, the overall degradation of DEA could be simply described by a pseudo first order reaction. The main degradation products were HEOD, THEED, and BHEP. It was concluded that C02 acted as a catalyst being neither consumed nor produced during the degradation of DEA to THEED and BHEP. HEOD was produced from DEA and C02, but was found to be unstable and could be converted back to DEA or react to form THEED and BHEP. The following simple kinetic model was developed to predict the degradation of DEA and the production of the major degradation compounds: [Figure 1] The model covered the ranges of DEA concentration 0-100 wt % DEA, 90-175°C, and C02 solubilities greater than 0.2 g C02/g DEA. Attempts were made to purify degraded DEA solutions. It has been claimed that activated carbon filters are useful in removing degradation compounds. However, tests with activated carbon proved it to be incapable of removing any of the major degradation compounds. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Over the past decade, membrane based gas separations have gained traction in industry as an attractive alternative to traditional thermally based separations due to their potential to offer lower operational and capital expenditures, greater ease of operation and lower environmental impact. As membrane research evolves, new state-of-the-art membrane materials as well as processes utilizing membranes will likely be developed. Therefore, their incorporation into existing thermally based units as a debottlenecking step or as a stand-alone separation unit is expected to become increasingly more common. Specifically for natural gas, utilization of smaller, more remote natural gas wells will require the use of less equipment intensive and more flexible separation technologies, which precludes the use of traditional, more capital and equipment intensive thermally based units. The use of membranes is, however, not without challenges. Perhaps the most important hurdle to overcome in membrane development for natural gas purification is the ability to maintain high efficiency in the presence of harsh feed components such as CO₂ and H₂S, both of which can swell and plasticize polymer membranes. Additionally, as this project demonstrates, achievement of similarly high selectivity for both CO₂ and H₂S is challenged by the different governing factors that control their transport through polymeric membranes. However, as others have suggested and shown, as well as what is demonstrated in this project, when CO₂ is the primary contaminant of interest, maintaining high CO₂/CH₄ efficiency appears to be more important in relation to product loss in the downstream. This work focuses on a class of fluorinated, glassy polyamide-imides which show high plasticization resistance without the need for covalent crosslinking. Membranes formed from various polyamide-imide materials show high mixed gas selectivities with adequate productivities when subjected to feed conditions that more closely resemble those that may be encountered in a real natural gas well. The results of this project highlight the polyamide-imide family as a promising platform for future membrane material development for materials aimed at aggressive natural gas purifications due to their ability to maintain high selectivities under aggressive feed conditions without the need for extensive stabilization methods.

Yes / Adsorbents are developing in the various separation industries; these adsorbents can use to sweeten natural gas and remove hydrogen sulfide. Many commercial adsorbents are not regenerable when exposed to hydrogen sulfide because hydrogen sulfide is highly reactive. For removal, the main challenge when using surface adsorbent, is the dissociation adsorption of and non-regenerability of adsorbent. In this study, ultra-stable Y (USY) zeolite, was chosen to adsorb hydrogen sulfide due to its unique physical and chemical properties. To accurately model the adsorption isotherms, experimental adsorption data were measured in high pressure up to 12 bar for hydrogen sulfide and 21 bar for carbon dioxide, methane, and nitrogen as other natural gas components. The experiments were performed at three temperatures of 283, 293 and 303 K. Toth model fitted the experimental data very well, and the capacity of hydrogen sulfide adsorption on USY at the temperature of 283 K and pressure of 12 bar is 4.47 mmol/g that is noticeable. By performing ten cycles of adsorption and regeneration of hydrogen sulfide on USY, the regenerability of the adsorbent was investigated and compared by conducting a similar test on commercial 13X adsorbent. USY is found to be completely regenerable when exposed to hydrogen sulfide. The Isosteric adsorption heat of hydrogen sulfide on the adsorbent is 18.1 kJ/mol, which indicates physical adsorption, and the order of adsorption capacity of tested compounds on USY is H2S > CO2≫CH4 > N2.