Conventional processes and membrane technology for carbon dioxide removal from natural gas:A review

Membrane technology is becoming more important for CO,_ separation from natural gas in the new era due to its process simplicity, relative ease of operation and control, compact, and easy to scale up as compared with conventional processes. Conventional processes such as absorption and adsorption for CO2 separation from natural gas are generally more energy demanding and costly for both operation and maintenance. Polymeric membranes are the current commercial membranes used for CO2 separation from natural gas. However, polymeric membranes possess drawbacks such as low permeability and selectivity, plasticization at high temperatures, as well as insufficient thermal and chemical stability. The shortcomings of commercial polymeric membranes have motivated researchers to opt for other alternatives, especially inorganic membranes due to their higher thermal stability, good chemical resistance to solvents, high mechanical strength and long lifetime. Surface modifications can be utilized in inorganic membranes to further enhance the selectivity, permeability or catalytic activities of the membrane. This paper is to provide a comprehensive review on gas separation, comparing membrane technology with other conventional methods of recovering CO2 from natural gas, challenges of current commercial polymeric membranes and inorganic membranes for CO2 removal and membrane surface modification for improved selectivity.

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed matrix membrane for CO_2 separation

In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.

Recent advances in multi-layer composite polymeric membranes for CO_2 separation: A review

The development of multilayer composite membranes for CO_2 separation has gained increasing attention due to the desire for energy efficient technologies. Multilayer composite membranes have many advantages, including the possibility to optimize membrane materials independently by layers according to their different functions and to reduce the overall transport resistance by using ultrathin selective layers, and less limitations on the material mechanical properties and processability. A comprehensive review is required to capture details of the progresses that have already been achieved in developing multilayer composite membranes with improved CO_2 separation performance in the past 15-20 years.In this review, various composite membrane preparation methods were compared, advances in composite membranes for CO_2/CH_4 separation,CO_2/N_2 and CO_2/H_2 separation were summarized with detailed data, and challenges facing for the CO_2 separation using composite membranes,such as aging, plasticization and long-term stability, were discussed. Finally the perspectives and future research directions for composite membranes were presented.

Hydrate-based carbon dioxide capture from simulated integrated gasification combined cycle gas

The equilibrium hydrate formation conditions for CO2/H2 gas mixtures with different CO2 concentrations in 0.29 mol% TBAB aqueous solution are firstly measured.The results illustrate that the equilibrium hydrate formation pressure increases remarkably with the decrease of CO2 concentration in the gas mixture.Based on the phase equilibrium data,a three stages hydrate CO2 separation from integrated gasification combined cycle （IGCC） synthesis gas is investigated.Because the separation efficiency is quite low for the third hydrate separation,a hybrid CO2 separation process of two hydrate stages in conjunction with one chemical absorption process （absorption with MEA） is proposed and studied.The experimental results show H2 concentration in the final residual gas released from the three stages hydrate CO2 separation process was approximately 95.0 mol% while that released from the hybrid CO2 separation process was approximately 99.4 mol%.Thus,the hybrid process is possible to be a promising technology for the industrial application in the future.

PVA/PVP blend polymer matrix for hosting carriers in facilitated transport membranes: Synergistic enhancement of CO2 separation performance

CO2 separation performance in facilitated transport membranes has been reported depended not only on the CO2 carrier properties but also to a great extent on the polymeric matrix regarding the capacity of retaining water and carriers as well as the processability for coating defect-free ultra-thin films. In this study, the blends of hydrophilic polymers polyvinyl pyrrolidone(PVP) and polyvinyl alcohol(PVA) were studied to find an optimal polymer matrix to host carriers in facilitated transport membranes for enhanced CO2 separation. It is found out that the optimized blend is 50/50 PVA/PVP by weight, which shows a significant increase in the water uptake(from 63 to 84%) at equilibrium state compared to the neat PVA. Polyethyleneimine(PEI) was employed to provide sample carriers to evaluate the synergistic effect of PVA and PVP on the CO2 separation performance. A thin film composite(TFC) membrane of the optimized blend(50/50 PVA/PVP with 50 wt% PEI) was fabricated on polysulfone(PSf) porous support. The fabrication of the TFC membranes is simple and low cost, and CO2 permeance of the optimized blend membrane is nearly doubled with the CO2/N2 selectivity remained unchanged, showing great potential for industrial applications of the resulted membranes.

Strain-controlled graphdiyne membrane for CO2/CH4 separation:First-principle and molecular dynamic simulation

Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance and mechanism of CO2/CH4 separation through strain-oriented graphdiyne(GDY)monolayer were studied by applying lateral strain.It is demonstrated that the CO2 permeance peaks at 1.29×10^6 gas permeation units(GPU)accompanied with CO2/CH4 selectivity of 5.27×10^3 under ultimate strain,both of which are far beyond the Robeson’s limit.Furthermore,the GDY membrane exhibited a decreasing gas diffusion energy barrier and increasing permeance with the increase of applied tensile strain.CO2 molecule tends to reoriented itself vertically to permeate the membrane.Finally,the CO2 permeability decreases with the increase of the temperature from300 K to 500 K due to conserving of rotational freedom,suggesting an abnormal permeance of CO2 in relation to temperature.Our theoretical results suggest that the stretchable GDY monolayer holds great promise to be an excellent candidate for CO2/CH4 separation,owing to its extremely high selectivity and permeability of CO2.

Separation of ionic liquids from dilute aqueous solutions using the method based on CO_2 hydrates

Ionic liquids （ILs） have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.

Synthesis of a PEBAX-1074/ZnO nanocomposite membrane with improved CO_2 separation performance

In this investigation, polymeric nanocomposite membranes（PNMs） were prepared via incorporating zinc oxide（ZnO） into poly（ether-block-amide）(PEBAX-1074) polymer matrix with different loadings. The neat membrane and nanocomposite membranes were prepared via solution casting and solution blending methods, respectively. The fabricated membranes were characterized by field emission scanning electron microscopy（FESEM） to survey cross-sectional morphologies and thermal gravimetric analysis（TGA）to study thermal stability. Fourier transform infrared（FT-IR） and X-ray diffraction（XRD） analyses were also employed to identify variations of the chemical bonds and crystal structure of the membranes, respectively. Permeation of pure gases, CO, CHand Nthrough the prepared neat and nanocomposite membranes was studied at pressures of 3–18 bar and temperature of 25 °C. The obtained results showed that the fabricated nanocomposite membranes exhibit better separation performance compared to the neat PEBAX membrane in terms of both permeability and selectivity. As an example, at temperature of 25 °C and pressure of 3 bar, COpermeability, ideal CO/CHand CO/Nselectivity values for the neat PEBAX membrane are 110.67 Barrer, 11.09 and 50.08, respectively, while those values are 152.27 Barrer,13.52 and 62.15 for PEBAX/ZnO nanocomposite membrane containing 8 wt% ZnO.

Solubilities of CO_2, CH_4,H_2,CO and N_2 in choline chloride/urea

Solubilities of CO_2, CH_4, H_2, CO and N_2 in choline chloride/urea(ChCl/Urea) were investigated at temperatures ranging from 308.2 to328.2 K and pressures ranging from 0.6 to 4.6 MPa. The results show that the solubilities of gases increase with increasing pressure and decreasing temperature. The solubility of CO_2 is higher than that of CH_4, H_2, CO and N_2, which indicates that ChCl/Urea may be used as a potential solvent for CO_2 capture from the gas mixture. Solubility of CO_2 in ChCl/Urea was fitted by Non-Random Two-Liquid and Redlich-Kwong(NRTL-RK) model, and solubility of CH_4, H_2, CO or N_2 in ChCl/Urea was fitted by Henry's Law. The standard enthalpy, standard Gibbs energy and standard entropy of gases were calculated. Additionally, the CO_2/CH_4 selectivities in water, dry ChCl/Urea and aqueous ChCl/Urea were further discussed.

Selective Permeation of CO_2 Through Modified PVSA/PS Composite Membrane

A new fixed carder membrane material VSA-SA for CO2 separation was prepared through the chemical modification of PVSA. The selective permeation of CO2 through VSA-SA/PS composite membrane was performed with CO2/CH4 system. The VSA-SA/PS composite membranes possess better CO2 permselectivity than PVSA/PS composite membrane. Keywords： Fixed carder membrane, CO2 separation, PVSA, VSA-SA.

Enhanced gas separation performance of mixed matrix hollow fiber membranes containing post-functionalized S-MIL-53

Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study,the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO2/CH4 separation performance of symmetric polysulfone membranes are investigated.Pure polysulfone membrane and ionic liquid-containing membranes are characterized.Field emission scanning electron microscopy(FE-SEM)is used to analyze surface morphology and thickness of the fabricated membranes.Energy dispersive spectroscopy(EDS)and elemental mapping,Fourier transform infrared(FTIR),thermal gravimetric(TGA),X-ray diffraction(XRD)and Tensile strength analyses are also conducted to characterize the prepared membrane s.CO2/CH4 separation performance of the membranes are measured twice at 0.3 MPa and room temperature(250 C).Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO2 permeation and CO2/CH4 selectivity due to high affinity of the ionic liquid to carbon dioxide.CO2 permeation significantly increases from 4,3 Barrer(1 Barrer=10^-10 cm^3(STP)·cm·m^-2·s^-1·cmHg^-1,1 cmHg=1.333 kPa)for the pure polymer membrane to 601.9 Barrer for the 30 wt%ionic liquid membrane.Also,selectivity of this membrane is improved from 8.2 to 25.8.mixed gas te sts are implemented to investigate gases interaction.The results showed,the disruptive effect of CH4 molecules for CO2 permeation lead to selectivity decrement compare to pure gas te st.The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO2/CH4 separation membranes.

Advances in high carbon dioxide separation performance of poly(ethylene oxide)-based membranes

Poly(ethylene-oxide)(PEO)-based membranes have attracted much attention recently for CO2 separation because CO2 is highly soluble into PEO and shows high selectivity over other gases such as CH4 and N2.Unfortunately,those membranes are not strong enough mechanically and highly crystalline,which hinders their broader applications for separation membranes.In this review discussions are made,as much in detail as possible,on the strategies to improve gas separation performance of PEO-based membranes.Some of techniques such as synthesis of graft copolymers that contain PEO,cross-linking of polymers and blending with long chains polymers contributed significantly to improvement of membrane.Incorporation of ionic liquids/nanoparticles has also been found effective.However,surface modification of nanoparticles has been done chemically or physically to enhance their compatibility with polymer matrix.As a result of all such efforts,an excellent performance,i.e.,CO2 permeability up to 200 Barrer,CO2/N2 selectivity up to 200 and CO2/CH4 selectivity up to 70,could be achieved.Another method is to introduce functional groups into PEO-based polymers which boosted CO2 permeability up to 200 Barrer with CO2/CH4 selectivity between 40 and 50.The CO2 permeability of PEO-based membranes increases,without much change in selectivity,when the length of ethylene oxide is increased.

Preparation of CO2 selective composite membranes using Pebax/CuBTC/PEG-ran-PPG ternary system

Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC（polymer/liquid/solid） was successfully deposited as a selective layer on a porous Polysulfone（PSF） support. In fact, the beneficial properties of PEG（high selectivity） with those of PPG（high permeability, amorphous） have been combined with superior properties of mixed matrix membrane（MMMs）. The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by COand CHadsorption test. Statistically based experimental design（central composite design, CCD） was applied to analyze and optimize the effect of PEG-ran-PPG（10–50 wt%） and CuBTC（0–20 wt%） mass contents on the COpermeance and CO/CHideal selectivity. Based on the regression coefficients of the obtained models, the COpermeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO/CHideal selectivity. Under the optimum conditions（PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%）, nearly 620% increase in the COpermeance and43% enhancement in the CO/CHideal selectivity was observed compared to the neat Pebax. The effect of pressure（3, 9 and 15 bar） on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of COin the membranes resulted in the enhancement of COpermeability with increase in gas pressure.

Fabrication of polymer/fluoride-containing salts blend composite membranes for CO_2 separation

Poly （N,N-dimethylaminoethyl methacrylate）-poly （ethylene glycol methyl ether methacrylate） （PDMAEMA-PEGMEMA） and cesium fluoride （CsF） were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone （PSf） hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU （1 GPU=10-6 cm3 （STP）/（cm 2 s cmHg））,and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride （KF）,due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.

First membrane unit for separating CO_2 from natural gas operational

After a more-than-two-week trial operation, a new membrane unit based on the technology developed by researchers from the CAS Dalian Institute of

Novel Porous Aromatic Framework with Excellent Separation Capability of CO2 in N2 or CH4

A novel porous aromatic framework, PAF-52, was obtained via the polymerization of tetrahedral mono- mer tetrakis（4-cyanodiphenyl） methane（TCDPM） with the aid of a facile ionothermal method. PAF-52 has a surface area of 1159 m2/g（BET）, and shows a considerable high separation ability of CO2 in N2 or CH4 respectively at room temperature, using gas-chromatography experiments as evidence,

Synthesis of porous aromatic framework with Friedel–Crafts alkylation reaction for CO_2 separation

A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel-Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area （785 m^2 g^-1） calculated from the Brunauer-Emmett-Teller （BET） model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.

Mixed-conducting ceramic–carbonate membranes exhibiting high CO2/O2 permeation flux and stability at high temperatures

This investigation demonstrates the feasibility to fabricate high quality ceramic–carbonate membranes based on mixed-conducting ceramics.Specifically,it is reported the simultaneous CO2/O2 permeation and stability properties of membranes constituted by a combination of ceramic and carbonate phases,wherein the microstructure of the ceramic part is composed,in turn,of a mixture of fluorite and perovskite phases.These ceramics showed ionic and electronic conduction,and at the operation temperature,the carbonate phase of the membranes is in liquid state,which allows the transport of CO32-and O2–species via different mechanisms.To fabricate the membranes,the ceramic powders were uniaxially pressed in a disk shape.Then,an incipient sintering treatment was carried out in such a way that a highly porous ceramic was obtained.Afterwards,the piece is densified by the infiltration of molten carbonate.Characterization of the membranes was accomplished by SEM,XRD,and gas permeation techniques among others.Thermal and chemical stability under an atmosphere rich in CO2 was evaluated.CO2/O2 permeation and long-term stability measurements were conducted between 850 and 940℃.The best permeation–separation performance of membranes of about 1 mm thickness,showed a maximum permeance flux of about 4.46×10^–7 mol·m^–2·s^–1·Pa^–1 for CO2 and 2.18×10^–7 mol·m^–2·s^–1·Pa^–1 for O2 at 940℃.Membranes exhibited separation factor values of 150–991 and 49–511 for CO2/N2 and O2/N2 respectively in the studied temperature range.Despite long-term stability test showed certain microstructural changes in the membranes,no significant detriment on the permeation properties was observed along 100 h of continuous operation.

Targeted synthesis of novel porous aromatic frameworks with selective separation of CO_2/CH_4and CO_2/N_2

Novel porous aromatic frameworks（PAF-53 and PAF-54） have been obtained by the polymerization of amino compound（p-phenylenediamine and melamine） and cyanuric chloride. They display a certain amount of CO2 adsorption capacity and highly selective separation of CO2/CH4 and CO2/N2 as 18.1 and83 by Henry Law respectively. They may be applied as ideal adsorbents to separate and capture CO2.