| Citation: |
XU Jingkai, GAO Qian, XIAO Wei, et al. Preparation and CH4/N2 separation performance of high permeability supported SBS membrane[J]. Acta Materiae Compositae Sinica, 2025, 42(5): 2670-2681.
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SBS block resin has a unique structure in which soft and hard segments are combined with each other, and gas molecules can be separated by extrusion. In this study, a series of x-SBS/Tetrahydrofuran (THF) resin solutions were used to prepare the corresponding SMS-x separation membranes with porous α-Al2O3 ceramics tubes as the carrier. FT-IR, XRD, SEM and other characterization test results show that the SBS resin can be well combined with the carrier, and the thickness of the separation membrane is less than 50 μm. The gas test shows that the SMS-20 separation membrane has the best CH4/N2 gas selectivity in the pressure range of 0.05-0.3 MPa. At 0.1 MPa, α(CH4/N2) =3.81, and the molar flux of CH4 is 1.41×10−6 mol·m−2·s−1·Pa−1. At 0.3 MPa, the CH4 molar flux of SMS-10 is the largest, which can reach 3.47×10−6 mol·m−2·s−1·Pa−1. In addition, the test of different proportions of mixed gas verifies that the separation membrane prepared in this paper can also be competent for the corresponding separation work. All the separation membranes prepared in this paper can stably separate gas for up to 7 days at a pressure difference of 0.1 MPa, and have good performance stability. Therefore, the porous α-Al2O3 substrate SBS separation membrane can have both excellent permeation flux and gas selectivity, and provide a favorable choice for the enrichment of coalbed methane CH4.
With the development of science and technology and the increasing demand for energy, the effective use of coal-bed methane is becoming more and more important. Using a safe, efficient, simple and low-cost method to concentrate and enrich CH in coal-bed methane will not only greatly alleviate the current energy shortage problem, but also reduce the concentration of CH in coal mine roadways and ensure safe production. Membrane separation method has the advantages of low energy consumption, simple operation and low cost in many CH/N separation technologies. Therefore, the separation of CH and N gas by membrane technology has been widely concerned by researchers.
A series of different composite membranes were prepared for CH/N separation by combining the advantages of the alternating soft and hard segments of the SBS block resin segment and the porous structure of α-AlO.In this paper, tetrahydrofuran(THF), styrene-butadiene-styrene block copolymer resin ( SBS 1301 ), porous α-AlO carrier tube support, anhydrous ethanol, deionized water and high purity N and CH gas were used as experimental materials. Firstly, THF solutions of SBS resins with different mass fractions were prepared, and then the α-AlO carrier tube was pretreated, including cleaning, ultrasonic treatment, drying and grinding. The pretreated carrier tube was immersed in SBS/THF solution for dip coating, and a uniform SMS series composite separation membrane was prepared. The particle size of SBS/THF resin solution and the structure, properties and morphology of SMS separation membrane were characterized by laser particle size analyzer, XRD, FT-IR and SEM. The single gas permeability test of the separation membrane was carried out using a gas permeability test device, and the permeability of N and CH at room temperature and different pressure conditions was tested.
The cross-sectional structure of different separation membranes was demonstrated by SEM images, including the cross-sectional morphology of blank α-AlO substrate and separation membranes ( SMS-10, SMS-15, SMS-20 ) prepared by different concentrations of SBS resin solution. The schematic diagram and SEM images of the film formation on the surface of the carrier were provided, and the formation process and structure of the membrane on the surface of the carrier were demonstrated. At the same time, the lattice and internal chemical bonds of the composite membrane were characterized by XRD and FT-IR. For the permeability of the composite membrane, the gas permeability of the separation membrane prepared by different concentrations of resin solution at 25℃ was studied under different conditions. It was found that the permeation flux of CH was 3 to 4 times that of N, and with the increase of resin concentration, the selectivity of the separation membrane increased, but the corresponding gas molar flux decreased.Under the pressure difference of 0.1 MPa, the single-component gas permeability SMS-20 achieved the highest selectivity of α(CH/N)=3.81, and the molar flux of CH was 1.41×10 mol·m·s·Pa. SMS-10 has the highest CH permeation flux of 3.47×10 mol·m·s·Pa at a pressure difference of 0.3 MPa. The permeability and CH/N selectivity of mixed gas with CH/N volume ratio of 50:50 and 15:85 were tested at 25℃ and 0.1 MPa pressure difference. It was found that the separation performance of mixed gas was lower than that of single gas, but the yield of composite membrane in mixed gas separation operation could reach the current average level.The performance stability of different separation membranes was tested for 4 h and 7 d at 25℃ and 0.1 MPa pressure difference. The results showed that all separation membranes could stably separate gas for up to 7 d and had good performance stability. At the same time, a series of mass transfer mechanism formulas were used to quantitatively investigate the dissolution and diffusion properties of the membrane, and the calculation results also supported the relevant conclusions of the gas permeability experiment.Conclusions:By using porous α-AlO ceramic tube as the carrier and combining with the gas separation membrane prepared by SBS/THF resin solution, under certain conditions, the α(CH/N) can reach 3.81, and the molar permeation flux of CH can reach 3.47×10 mol·m·s·Pa. In addition, the separation membrane can maintain superior performance under different proportions of mixed gas tests and long-term stability tests. The results show that the porous α-AlO supported SBS separation membrane has a good application prospect in the enrichment of coal-bed methane CH, and can provide excellent permeation flux and gas selectivity. At the same time, the research in this paper provides a new idea for the follow-up research and development of gas separation membranes, that is, by reducing the thickness of the membrane to reduce the gas transfer distance inside the membrane, thereby increasing the permeation flux.
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