Impact of sulphur contamination on the performance of mixed ionic-electronic conducting membranes for oxygen separation and hydrogen production

PhD ThesisMixed ionic-electronic conducting (MIEC) membranes are a promising technology for oxygen separation but they are not commercialised yet due to sealing issue and sensitivity to impurities in feedstock. In this study, La0.6Sr0.4Co0.2Fe0.8O3- (LSCF6428) was successfully sealed for long-term operation of 963 h using a gold-glass-ceramic sealant. The membrane was then tested for air separation in presence of hydrogen sulphide for 100 h and results showed that the impurity caused a drop in oxygen flux to zero within few hours. The flux could not be fully restored after hydrogen sulphide removal and only 6 to 35% was recovered. It was proposed that hydrogen sulphide was adsorbed on the membrane in the form of sulphur and it occupied oxygen vacancies. With time, strontium segregates toward sulphur to form irreversible layer of strontium sulphate. To restore the damaged surface, the membrane was treated by 1% (mol) of hydrogen for 20 h and the recovery improved from 6 to 12%. It was discovered that the poisoning mechanism is a function of oxygen partial pressure and change of partial pressure from 0.21 to 0.01 bar resulted in 90% recovery and this can be used as a strategy to reduce the damage. The next step was to test the membrane for hydrogen production using 1% (mol) of methane and results showed that methane conversion was steady at 33% for 350 h. Methane oxidation was also carried in presence of hydrogen sulphide but it resulted in drop of conversion to 8%. However, the conversion was slowly regenerating with time and it reached a constant value of 15%. This recovery was interpreted by the reaction of methane with hydrogen sulphide or methane decomposition and the membrane acted as a catalyst for these reactions. After hydrogen sulphide removal from the feed, the conversion kept on decreasing and this was linked to the change of membrane properties and therefore the membrane could not provide the sites for methane-oxygen reaction. For better stability under hydrogen sulphide, the membrane was modified by adding a powder of LSCF6428 material over the dense membrane. This dual layer membrane was stable for air separation under hydrogen for 33 h and the flux was only reduced by 5%

Polymeric Gas-Separation Membranes for Petroleum Refining

Polymeric gas-separation membranes were commercialized 30 years ago. The interest on these systems is increasing because of the simplicity of concept and low-energy consumption. In the refinery, gas separation is needed in many processes such as natural gas treatment, carbon dioxide capture, hydrogen purification, and hydrocarbons separations. In these processes, the membranes have proven to be a potential candidate to replace the current conventional methods of amine scrubbing, pressure swing adsorption, and cryogenic distillation. In this paper, applications of polymeric membranes in the refinery are discussed by reviewing current materials and commercialized units. Economical evaluation of these membranes in comparison to traditional processes is also indicated

Microscopy and Spectroscopy Techniques for Characterization of Polymeric Membranes

Polymeric membrane is a proven technology for water purification and wastewater treatment. The membrane is also commercialized for gas separation, mainly for carbon dioxide removal and hydrogen recovery. Characterization techniques are excellent tools for exploring the membrane structure and the chemical properties. This information can be then optimized to improve the membrane for better performance. In this paper, characterization techniques for studying the physical structure such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are discussed. Techniques for investigating the crystal structure such as X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS) are also considered. Other tools for determining the functional groups such Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and nuclear magnetic resonance (NMR) are reviewed. Methods for determining the elemental composition such as energy-dispersion X-ray spectroscopy (EDS), X-ray fluorescent (XRF), and X-ray photoelectron spectroscopy (XPS) are explored. The paper also gives general guidelines for sample preparation and data interpretation for each characterization technique

Accuracy of Mathematical Models and Process Simulators for Predicting the Performance of Gas-Separation Membranes

A membrane unit for gas separation is not available in most process simulators, and therefore it needs to be built manually. However, the developed units are based on assumptions, and the system is solved numerically. The accuracy of these models with industrial data is rarely discussed in the literature, but it is needed to confirm the reliability of process simulators. In this work, the membrane unit was developed in two different simulation software such as the commercial UniSIM® and the freeware CAPE-OPEN to CAPE-OPEN (COCO). In UniSIM®, the membrane module was built internally using a component splitter, spreadsheet, and adjust functions. In COCO, the membrane unit was developed by program coding with the external computational software, Scilab. The developed membrane units were assessed with field data for fuel gas conditioning. Results show that the membrane unit was easier to build in UniSIM® but when calculating the flowrate and composition of all compounds at the permeate and retentate sides, UniSIM® gives an error of 17.4% while COCO gives a slightly lower error of 17.1%. The high error was related to the effects of plasticization and concentration polarization, which were not taken into consideration in the mathematical model

Oxygen Enrichment Membranes for Kuwait Power Plants: A Case Study

Power plants are considered as the major source of carbon dioxide pollution in Kuwait. The gas is released from the combustion of fuel with air to convert water into steam. It has been proven that the use of enriched oxygen can reduce fuel consumption and minimize emissions. In this study, UniSim (Honeywell, Charlotte, NC, USA) was used to estimate the fuel savings and carbon dioxide emissions of the largest power plant in Kuwait (Alzour). Results showed that at 30 mol% oxygen, the fuel consumption was lowered by 8%, with a reduction in carbon dioxide emissions by 3524 tons per day. An economic analysis was performed on the use of a membrane unit to produce 30 mol% oxygen. At current market prices, the unit is not economical. However, the system can achieve a payback duration of 3 years if natural gas price increases to USD 6.74 or the compressor cost decreases to USD 52 per kW. Currently, the research and development sector is targeting a membrane fabrication cost of less than USD 10 per m2 to make the membrane process more attractive

Optimization of Mordenite Membranes Using Sucrose Precursor for Pervaporation of Water-Ethanol Mixtures

Post-treated mordenite membranes were prepared using sucrose (C12H22O11) as a carbon precursor to block any pinholes and defects in the zeolite layer. The pervaporation (PV) process was used to separate ethanol from the water. The effects of the sucrose concentration and the pyrolysis temperature (650–850 °C) were investigated, and the resulting high separation performance compared to those post/pre-treated membranes was reported in the literature. In this study, mordenite carbon membranes yielded a water/ethanol separation factor of 990.37 at a water flux of 9.10 g/m2h. The influence of the operating temperature on the performance of the membrane also was considered. It was concluded that the selective adsorption of water through zeolite pores was achieved. The entire preparation procedure was achieved using a rapid, low-cost preparation process

Microscopy and Spectroscopy Techniques for Characterization of Polymeric Membranes

Polymeric membrane is a proven technology for water purification and wastewater treatment. The membrane is also commercialized for gas separation, mainly for carbon dioxide removal and hydrogen recovery. Characterization techniques are excellent tools for exploring the membrane structure and the chemical properties. This information can be then optimized to improve the membrane for better performance. In this paper, characterization techniques for studying the physical structure such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are discussed. Techniques for investigating the crystal structure such as X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS) are also considered. Other tools for determining the functional groups such Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and nuclear magnetic resonance (NMR) are reviewed. Methods for determining the elemental composition such as energy-dispersion X-ray spectroscopy (EDS), X-ray fluorescent (XRF), and X-ray photoelectron spectroscopy (XPS) are explored. The paper also gives general guidelines for sample preparation and data interpretation for each characterization technique.</jats:p