Membrane-based gas separation

The membrane gas separation industry is 35 years old and growing at a significant rate. Development of higher selectivity and higher permeance membranes would result in faster growth. This paper will analyze the barriers that have inhibited the development of these membranes. We start by reviewing the lessons that can be drawn from the past 35 years of experience. We then review the needs and most promising research directions for new materials in current and future membrane applications.

Gas Separation Membrane Materials: A Perspective

Membrane processes have evolved as a competitive approach in CO2 separations compared with absorption and adsorption processes, due to their inherent attributes such as energy-saving and continuous operation. High permeability membrane materials are crucial to efficient membrane processes. Among existing membrane materials for CO2 separations, polymer-based materials have some intrinsic advantages such as good processability, low price and a readily available variety of materials. In recent years, enormous research effort has been devoted to the use of membrane technology for CO2 separations from diverse sources such as flue gas (mainly N2), natural gas (mainly CH4) and syngas (mainly H2). Polymer-based membrane materials occupy the vast majority of all the membrane materials. For large-scale CO2 separations, polymer-based membrane materials with high CO2 permeability and good CO2/gas selectivity are required. In 2012, we published a Perspective review in Energy & Environmental Science on high permeability polymeric membrane materials for CO2 separations. Since then, more rapid progress has been made and the research focus has changed significantly. This review summarises the advances since 2012 on high permeability polymer-based membrane materials for CO2 separations. The major features of this review are reflected in the following three aspects: (1) we cover polymer-based membrane materials instead of purely polymeric membrane materials, which encompass both polymeric membranes and polymer–inorganic hybrid membranes. (2) CO2 facilitated transport membrane materials are presented. (3) Biomimetism and bioinspired membrane concepts are incorporated. A number of representative examples of recent advances in high permeability polymer-based membrane materials is highlighted with some critical analysis, followed by a brief perspective on future research and development directions.

Advances in high permeability polymer-based membrane materials for CO2 separations

Polyvinylamine (PVAm) was modified using a cross-linking agent containing carriers piperazine (PIP). Attenuated total reflectance fourier transform infrared, elemental analyzer, and X-ray diffraction were used to characterize the PIP-modified PVAm. The PVAm–PIP/polysulfone (PS) composite membrane was developed by coating PVAm–PIP mixed solutions with different mass ratios of PIP/PVAm (mPIP/mPVAm) on the PS ultrafiltration membrane. The effects of mPIP/mPVAm (from 0.715 to 2.860) in the coating solutions and wet coating thickness on the gas performance of the PVAm–PIP/PS composite membrane were investigated. The PVAm–PIP/PS composite membrane prepared showed higher performance than other membranes reported in the literature due to the large increase of the introducing carrier concentration and low crystallinity. Moreover, the separation performance stability of the PVAm–PIP/PS composite membrane was investigated and no deterioration in the membrane permselectivity was observed. Finally, the economic evaluation of the membrane with the highest performance prepared was carried out. © 2012 American Institute of Chemical Engineers AIChE J, 59: 215–228, 2013

PVAm–PIP/PS Composite Membrane with High Performance for CO2/N2 Separation

Surface characterization by FTIR-ATR spectroscopy of polyethersulfone membranes-unmodified, modified and protein fouled

Miniaturization and manipulation of materials at nanometer scale are key challenges in nanoscience and nanotechnology. In membrane science and technology, the fabrication of ultra-thin polymer films (defect-free) on square meter scale with uniform thickness ( 5 m3 (STP) m − 2 h − 1 bar − 1. The permeances are extremely high, because the membranes are made from a CO2 philic polymer material and they are only a few tens of nanometers thin. Thus, these thin film membranes have potential application in the treatment of large gas streams under low pressure like, e.g., carbon dioxide separation from flue gas.

https://iopscience.iop.org/article/10.1088/0957-4484/21/39/395301/pdf

Nanometric thin film membranes manufactured on square meter scale: ultra-thin films for CO2 capture

Asymmetric gas separation membranes were prepared by a dry/wet phase inversion process using poly(ether sulfone) as membrane-forming material. Variations in the composition of multicomponent casting solutions and choice of the coagulation medium resulted in membranes with drastically different gas separation properties. Optimized integral-asymmetric poly(ether sulfone) membranes coagulated in methanol had pressure-normalized CO 2 fluxes of 7.2×10 -5 cm 3 (STP)/(cm 2 .s.cmHg) and a CO 2 /N 2 selectivity of 40. However, asymmetric membranes coated with a thin layer of silicone rubber showed substantially improved gas separation performance. Poly(ether sulfone)/silicone multicomponent membranes showed pressure-normalized CO 2 fluxes of up to 6.2×10 -5 cm 3 (STP)/(cm 2 .s.cmHg) combined with a CO 2 /N 2 selectivity of 60, essentially equal to the intrinsic permselectivity of poly(ether sulfone)

Ultrathin multicomponent poly(ether sulfone) membranes for gas separation made by dry/wet phase inversion

Process for separating and/or recovering gases from gas and/ or gas vapour mixtures (11) by means of a membrane separating device (12, 16) to which the gasand/or gas vapour mixture (11) is supplied, the latter being separated in the membrane separating device (12, 16) into a permeate (14, 18), which is enriched with gas, and a retentate (13, 17), which is deplet-ed of gas. A first membrane separating device (b) (12) and a downstream second membrane separating device (a) (16) are provided, to which is supplied (at its inlet end) the retentate (13) from the first membrane separating device (b) (12), the first membrane separating device (b) (12) having a membrane (15) which is selective for higher hydrocarbons in the gas and/or gas vapour mixture (11) to be separated and in that the second membrane separating device (a) ( 16) has a membrane (19) which is selective for gases of small molecular diameter.

Multi-stage process for the separation/recovery of gases

A method for producing an improved membrane for separating gases in mixtures including forming an integral, asymmetric polyether imide membrane, treating the membrane with at least one organic fluid which is a solvent or swelling agent for polyether imide, and removing the organic fluid from the membrane by evaporation to obtain a tubular, flat or hollow fiber membrane exhibiting significantly higher selectivity than an untreated membrane.

Process for enhancing the selectivity of asymmetric membranes

The emissions generated by car refueling are caught and returned to the gasoline storage tanks by a vacuum assisted vapor return. Emissions vented via breather pipe of the storage tanks have been treated by hydrocarbon vapor selective membranes. A pilot plant, based on this principle, has been evaluated by the TÜV Rheinland. An overall emission reduction of higher than 93 % has been proven and certified.

New technology for emission reduction at petrol stations : Membrane technology in petrolum, petrochemical and gas processing

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