Poly (4-methyl-2-pentyne) (PMPentyne) and poly (4-methyl-1-pentene) (PMPentene) as membrane gas-separating media were studied with a combination of experimental and theoretical approaches. Experimental approaches included the permeability measurements for C₁–C₄ alkanes in linear heating mode (for PMPentyne) and under isothermal conditions (for PMPentene), and diffusivity evaluation by a differential method for PMPentene. Theoretical approaches included the ‘hard-spheres’ theory for calculation of gas solubility in PMPentyne and gas transport theory for two-phase systems for the estimation of the amorphous and crystalline phases contribution in PMPentene. Correlation analysis was used for any type of gas transfer parameter calculation where experimental data were lacking. These combinations of methods allowed obtaining the whole set of parameters for any gas–polymer pairing and explained the butane-selective properties revealed in PMPentyne (C₁ < C₂ < C₃ < C₄) and methane-selective properties of PMPentene (C₁ > C₂ > C₃ > C₄).

This study presents a comprehensive evaluation of a modified membrane cascade operating in “Continuous Membrane Column” mode for selective CO₂ capture in combined heat power plants. For the first time, a novel membrane cascade configuration for separating four-component wet flue gases is analyzed and compared with existing technologies in terms of the capital and operating costs required to capture one ton of CO₂. The proposed membrane cascade generates two countercurrent recirculating streams: one continuously depleted of the permeate component and the other enriched in it. Because the internal recirculation streams significantly exceed the bypass product streams, the system demonstrates a multiplicative increase in separation efficiency. As a result, the required membrane area and compression energy can be significantly reduced. The analysis demonstrates that the proposed cascade configuration meets all current performance requirements for CO₂ recovery and the target composition of the product and residual streams. Furthermore, due to its balanced material and energy cost ratio, the system can serve as a competitive alternative to previously developed membrane CO₂ capture technologies, offering lower overall capture losses.

Hybrid gas separation technologies combining different physicochemical mechanisms represent a promising approach for the efficient treatment of complex natural gas mixtures. In this work, a hybrid process integrating gas hydrate crystallization and membrane gas separation was investigated for the upgrading of multicomponent natural gas-containing hydrocarbons (C₁–C₄), acid gases (CO₂ and H₂S), and inert components. Polysulfone hollow-fiber membranes were fabricated, and their gas transport properties were experimentally determined using an eight-component quasi-real natural gas mixture under elevated pressure conditions. The obtained mixed-gas permeance values were used as input parameters for the development of a detailed mathematical model of a hollow-fiber membrane module implemented in the Aspen Custom Modeler. The model was applied to simulate membrane separation of both gas- and hydrate-derived streams produced by the gas hydrate crystallizer. Simulation results were analyzed in terms of hydrocarbon composition, acid gas removal efficiency, and hydrocarbon recovery as a function of the stage-cut. The modeling predictions were validated experimentally using a laboratory membrane module integrated with the gas hydrate crystallization unit. Good agreement between the experimental data and simulation results was observed for all major components. The deviation between modeled and experimental concentrations remained small, while the discrepancy in hydrocarbon recovery was higher and reached approximately 10–20%, which is attributed to the cumulative uncertainty of flow rate and composition measurements. These results confirm the adequacy of the developed model. The hybrid process demonstrates strong complementarity between the thermodynamic selectivity of hydrate formation and the transport selectivity of membrane separation, enabling efficient removal of acid gases while maintaining acceptable hydrocarbon recovery. The results indicate that the proposed gas hydrate–membrane hybrid process is a promising strategy for advanced natural gas purification and upgrading.

Biogas upgrading to biomethane is an important route for increasing the energy value of renewable gas streams and enabling their wider use in fuel, heat, and power applications. In the present study, a two-stage membrane process for biogas upgrading was developed and validated using polysulfone (PSF) and polyetherimide (PEI) hollow-fiber membranes. The main original aspects of this work include the formulation of a PEI/DMF/IPA spinning dope composition (27/60/13 wt.%), the mixed-gas testing of PSF and PEI hollow-fiber membranes in a six-component model biogas mixture, and the combined simulation, experimental validation, and techno-economic evaluation of a two-stage membrane process. Mixed-gas permeation experiments with a six-component model biogas mixture were used as the basis for process simulation of four membrane-stage configurations. Only the PSF + PEI cascade simultaneously provided methane recovery above 90%, methane concentration in the product above 95 mol.%, and residual carbon dioxide content below 2 mol.%. Experimental verification confirmed the modeled process concept and demonstrated that the target biomethane quality was achieved at feed flow rates of 0.9–1.1 L min⁻¹, where methane recovery reached 93.5–95.2% and methane purity was 95.5–96.2 mol.%. A preliminary techno-economic analysis for a 100 m³ h⁻¹ unit indicated an upgrading penalty of USD 96.4 per ton of 95.5 mol.% CH₄. PSF membranes provided higher carbon dioxide permeance, whereas PEI membranes exhibited higher CO₂/CH₄ selectivity, which explains the efficiency of their combination in the two-stage scheme. The results show that the proposed PSF + PEI cascade is a promising membrane-based approach for energy-efficient biogas upgrading.