CO2 removal by single and mixed amines in a hollow‐fiber membrane module—investigation of contactor performance

This work investigates CO₂ removal by single and blended amines in a hollow‐fiber membrane contactor (HFMC) under gas‐filled and partially liquid‐filled membrane pores conditions via a two‐scale, nonisothermal, steady‐state model accounting for CO₂ diffusion in gas‐filled pores, CO₂ and amines diffusion/reaction within liquid‐filled pores and CO₂ and amines diffusion/reaction in liquid boundary layer. Model predictions were compared with CO₂ absorption data under various experimental conditions. The model was used to analyze the effects of liquid and gas velocity, CO₂ partial pressure, single (primary, secondary, tertiary, and sterically hindered alkanolamines) and mixed amines solution type, membrane wetting, and cocurrent/countercurrent flow orientation on the HFMC performance. An insignificant difference between the absorption in cocurrent and countercurrent flow was observed in this study. The membrane wetting decreases significantly the performance of hollow‐fiber membrane module. The nonisothermal simulations reveal that the hollow‐fiber membrane module operation can be considered as nearly isothermal. © 2014 American Institute of Chemical Engineers AIChE J, 61: 955–971, 2015     

Modeling of CO2 mass transport across a hollow fiber membrane reactor filled with immobilized enzyme

The enzyme‐based contained liquid membrane reactor to capture CO₂ from the closed spaces is a very complicated process with large numbers of interdependent variables. A theoretical and experimental analysis of facilitated transport of CO₂ across a hollow fiber membrane reactor filled with immobilized carbonic anhydrase (CA) by nanocomposite hydrogel was presented. CO₂ concentration profiles in the feed gas phase and the membrane wall were achieved by numeric simulation. The effects of CO₂ concentration, CA concentration, and flow rate of feed gas on CO₂ removal performance were studied in detail, and the model solution agrees with the experimental data with a maximum deviation of up to 18.7%. Moreover, the effect of CO₂ concentration on the required membrane areas for the same CO₂ removal target (1 kg/day) was also investigated. This could provide real‐world data and scientific basis for future development toward a final efficient CO₂ removal device. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Prediction of CO2 gas permeability behavior of ionic liquid–polymer membranes (ILPM)

Predicting the gas permeability of ionic liquid‐polymeric membranes (ILPM) is of great importance for the design of efficient gas separation membrane materials. The available models for the prediction of CO₂ gas permeability through ionic liquid‐polymeric membranes were analyzed using the literature data. Maxwell model was selected for modification due to relatively accurate prediction capability. The Maxwell model was modified for ionic liquid‐polymeric membranes by incorporating model parameter k for the effectiveness of volume fraction of dispersed phase. The established methodology was tested for different ionic liquid‐polymeric membrane systems for validation. A satisfactory agreement was observed for predicted and experimental permeability by using the current approach. This method can be used for the prediction of CO₂ gas permeability through ionic liquid‐polymeric membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44761.     

Enhancing CO2 absorption efficiency using a novel PTFE hollow fiber membrane contactor at elevated pressure

The internal structure design of membrane module is very important for gas removal performance using membrane contactor via physical absorption. In this study, a novel membrane contactor developed by weaving polytetrafluoroethylene (PTFE) hollow fibers was applied to remove CO₂ from 60% N₂ + 40% CO₂ mixture (with CO₂ concentration similar to that of biogas) at elevated pressure (0.8 MPa) using water as absorbent. Compared with the conventional module with randomly packed straight fibers, the module with woven PTFE fibers exhibited much better CO₂ absorption performance. The weaving configuration facilitated the meandering flow or Dean vortices and renewing speed of water around hollow fibers. Meanwhile, the undesired influences such as channeling and bypassing were also eliminated. Consequently, the mass transfer of liquid phase was greatly improved and the CO₂ removal efficiency was significantly enhanced. The effects of operation pressure, module arrangement, feed gas, and water flow rate on CO₂ removal were systematically investigated as well. The overall mass‐transfer coefficient (K_OV) varied from 1.96 × 10^?5 to 4.39 × 10^?5 m/s (the volumetric mass‐transfer coefficient K_La = 0.034–0.075 s^?1) under the experimental conditions. The CO₂ removal performance of novel woven fiber membrane contactor matched well with the simulation results. © 2017 American Institute of Chemical Engineers AIChE J, 64: 2135–2145, 2018     

The use of carbonic anhydrase to accelerate carbon dioxide capture processes

The chemical absorption of CO₂ into a monoethanolamine solvent is currently the most widely accepted commercial approach to carbon dioxide capture. However, the subsequent desorption of CO₂ from the solvents is extremely energy intensive. Alternative solvents are more energy efficient, but their slow reaction kinetics in the CO₂ absorption step limits application. The use of a carbonic anhydrase (CA) enzyme as a reaction promoter can potentially overcome this obstacle. Native, engineered and artificial CA enzymes have been investigated for this application. Immobilization of the enzyme within the gas absorber or in a membrane format can increase enzyme stability and avoid thermal denaturation in the stripper. However, immobilization is only effective if the mass transfer of carbon dioxide through the liquid phase to reach the immobilization substrate does not become rate controlling. Further research should also consider the process economics of large‐scale enzyme production and the long‐term performance of the enzyme under real flue gas conditions. © 2014 Society of Chemical Industry     

Enhanced CO2 separation performance by PVA/PEG/silica mixed matrix membrane

This article focused on segregation of low concentration CO₂ from CO₂/N₂ mixture gas by implementing high‐performance facilitated transport mixed matrix membranes (MMMs) in large‐scale carbon capture techniques. These advanced, novel CO₂‐selective membrane materials were developed by embedding silica nanoparticles at different loading into the poly(vinyl alcohol) (PVA)/poly(ethylene glycol) (PEG) matrix using solution casting. In situ sol–gel technique was applied for the synthesis of the hydrophilic SiO₂ nanoparticles. The compatibility of filler‐polymer matrix plays a crucial role in the optimization of the membrane performance. The dispersion and interaction of the filler into the polymer matrix were confirmed by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy, contact angle tests, and swelling ratio analysis. Field emission scanning electron microscopy analysis of the synthesized MMMs established the homogeneous dispersion of the fillers in the polymer matrix. Owing to its good compatibility with PVA/PEG matrix, the inclusion of fillers significantly increased the overall separation efficiency of CO₂ within the membrane. Compared to pristine PVA/PEG membrane, PVA/PEG/silica membrane with 3.34 wt % silica loading showed pronounced improvement in its gas separation properties with 78% augmentation in CO₂ permeability and 45% enhancement in CO₂/N₂ selectivity for fixed conditions pertaining to sweep side water flow rate of 0.04 mL/min and 100 °C temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46481.     

Synthesis and optimization of membrane cascade for gas separation via mixed‐integer nonlinear programming

Currently, membrane gas separation systems enjoy widespread acceptance in industry as multistage systems are needed to achieve high recovery and high product purity simultaneously, many such configurations are possible. These designs rely on the process engineer's experience and therefore suboptimal configurations are often the result. This article proposes a systematic methodology for obtaining the optimal multistage membrane flow sheet and corresponding operating conditions. The new approach is applied to cross‐flow membrane modules that separate CO₂ from CH₄, for which the optimization of the proposed superstructure has been achieved via a mixed‐integer nonlinear programming model, with the gas processing cost as objective function. The novelty of this work resides in the large number of possible interconnections between each membrane module, the energy recovery from the high pressure outlet stream and allowing for nonisothermal conditions. The results presented in this work comprise the optimal flow sheet and operating conditions of two case studies. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1989–2006, 2017     

Oxy‐fuel combustion for CO2 capture using a CO2‐tolerant oxygen transporting membrane

CO₂ capture via an oxy‐fuel route through the U‐shaped (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) hollow fiber membrane with 100% CH₄ conversion and 100% CO₂ selectivity for 450 h has been explored for the first time. X‐ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy characterizations of the spent hollow fiber membrane have also been investigated. All these results indicate that PLNCG hollow fiber membrane shows excellent reaction performance and good stability under oxy‐fuel reaction conditions, which will be a potential rounte for reducing CO₂ emissions worldwide. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3856–3862, 2013     

Mass transfer performance and correlations for CO2 absorption into aqueous blended of DEEA/MEA in a random packed column

The mass transfer performance of CO₂ absorption into blended N,N‐diethylethanolamine (DEEA)/ethanolamine (MEA) solutions was investigated using a lab‐scale absorber (H = 1.28 m, D = 28 mm) packed with Dixon ring random packing. The mass transfer coefficient K_Ga_v, the unit volume absorption rate Φ, outlet concentration of CO₂ (y_CO2), and the bottom temperature T_bot of CO₂ in aqueous DEEA/MEA solutions were determined over the feed temperature range of 298.15–323.15 K, lean CO₂ loading of 0.15–0.31 mol/mol, over a wide range of liquid flow rate of 3.90–9.75 m³/m²‐h, by using inert gas flow rate of 26.11–39.17 kmol/m²‐h and 6–18 kPa CO₂ partial pressure. The results show that liquid feed temperature, lean CO₂ loading, liquid flow rate, and CO₂ partial pressure had significant effect on those parameters. However, the inert gas flow rate had little effect. To allow the mass transfer data to be really utilized, K_Ga_v and y_out correlations for the prediction of mass transfer performance were proposed and discussed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3048–3057, 2017     

Size effects of graphene oxide on mixed matrix membranes for CO2 separation

Graphene oxide (GO)‐polyether block amide (PEBA) mixed matrix membranes were fabricated and the effects of GO lateral size on membranes morphologies, microstructures, physicochemical properties, and gas separation performances were systematically investigated. By varying the GO lateral sizes (100–200 nm, 1–2 μm, and 5–10 μm), the polymer chains mobility, as well as the length of the gas channels could be effectively manipulated. Among the as‐prepared membranes, a GO‐PEBA mixed matrix membrane (GO‐M‐PEBA) containing 0.1 wt % medium‐lateral sized (1–2 μm) GO sheets showed the highest CO₂ permeation performance (CO₂ permeability of 110 Barrer and CO₂/N₂ mixed gas selectivity of 80), which transcends the Robeson upper bound. Also, this GO‐PEBA mixed matrix membrane exhibited high stability during long‐term operation testing. Optimized by GO lateral size, the developed GO‐PEBA mixed matrix membrane shows promising potential for industrial implementation of efficient CO₂ capture. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2843–2852, 2016     

A highly stable metal‐organic framework with optimum aperture size for CO2 capture

We herein report an optimal modulated hydrothermal (MHT) synthesis of a highly stable zirconium metal‐organic framework (MOF) with an optimum aperture size of 3.93 Å that is favorable for CO₂ adsorption. It exhibits excellent CO₂ uptake capacities of 2.50 and 5.63 mmol g^?1 under 0.15 and 1 bar at 298 K, respectively, which are among the highest of all the pristine water‐stable MOFs reported so far. In addition, we have designed a lab‐scale breakthrough set‐up to study its CO₂ capture performance under both dry and wet conditions. The velocity at the exit of breakthrough column for mass balance accuracy is carefully measured using argon with a fixed flow rate as the internal reference. Other factors that may affect the breakthrough dynamics, such as pressure drop and its impact on the roll‐up of the weaker component have been studied in details. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4103–4114, 2017     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

Calix[4]arene‐filled poly dimethylsiloxane (PDMS) membranes for the pervaporative removal of benzene from dilute aqueous solution

In this article, tert‐butylcalix [4]arene (CA)‐filled poly dimethylsiloxane (PDMS) membranes (CA‐f‐PDMS) were prepared for pervaporative removal of benzene from aqueous solution. In comparison with unfilled PDMS membrane, CA‐f‐PDMS membranes showed higher permselectivity towards benzene due to the inclusion interaction between benzene and CA. The separation factor increased from 3275 to 5604 when the CA content varies from 0 to 3 wt % in the PDMS membrane. On the other hand, the normalized permeation rate of benzene (NPR_b) decreased with the increase of the degree of crystallization of the membranes due to the crystallinity of CA. The membrane with 1 wt % CA content had the highest degree of crystallization and thus the lowest NPR_b, whereas the membrane with 3 wt % CA content was the opposite. Furthermore, the addition of CA increased the elastic modulus of membranes slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 90–100, 2006     

Chemical solvent in chemical solvent: A class of hybrid materials for effective capture of CO2

Amino acid ionic liquids (AAILs) are chemical solvents with high reactivity to CO₂. However, they suffer from drastic increase in viscosity on the reaction with CO₂, which significantly limits their application in the industrial capture of CO₂. In this work, 1‐ethyl‐3‐methylimidazolium acetate ([emim][Ac]) which also exhibits chemical affinity to CO₂ but low viscosity, and its viscosity does not increase drastically after CO₂ absorption, was proposed as the diluent for AAILs to fabricate hybrid materials. The AAIL+[emim][Ac] hybrids were found to display enhanced kinetics for CO₂ absorption, and their viscosity increase after CO₂ absorption are much less significant than pure AAILs. More importantly, owing to the fact that [emim][Ac] itself can absorb large amount of CO₂, the AAIL+[emim][Ac] hybrids still have high absolute capacities of CO₂. Such hybrid materials consisting of a chemical solvent plus another chemical solvent are believed to be a class of effective absorbents for CO₂ capture. © 2017 American Institute of Chemical Engineers AIChE J, 64: 632–639, 2018     

Hydrophobic and tribological behaviors of a poly(p‐phenylene benzobisoxazole) fabric composite reinforced with nano‐TiO2

1H,1H,2H,2H‐Perfluorooctyl trichlorosilane (PFTS) was used to modify TiO₂ nanoparticles, and hydrophobic PFTS–TiO₂ nanoparticles were obtained by an ultrasonic reaction method. The PFTS–TiO₂ surface morphological and hydrophobic properties were analyzed with scanning electron microscopy (SEM), Fourier transform infrared spectrometry, and contact angle (CA) testing. Then, the poly(p‐phenylene benzobisoxazole) fabric–phenolic composite filled with PFTS–TiO₂ as a lubricant additive was fabricated by a dip‐coating process. The tribological properties of the composite were investigated, and the wear surface morphology was observed by SEM. The experimental results show that the water CA of the composite filled with PFTS–TiO₂ was 158°, and the composite containing 4 wt % PFTS–TiO₂ exhibited excellent antifriction and abrasion resistance. The hydrophobic surface of the composite showed excellent durable performance with a static water CA of 126.7° after abrasion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45077.     

Hybrid FSC membrane for CO2 removal from natural gas: Experimental,process simulation,and economic feasibility analysis

The novel fixed‐site‐carrier (FSC) membranes were prepared by coating carbon nanotubes reinforced polyvinylamine/polyvinyl alcohol selective layer on top of ultrafiltration polysulfone support. Small pilot‐scale modules with membrane area of 110–330 cm² were tested with high pressure permeation rig. The prepared hybrid FSC membranes show high CO₂ permeance of 0.084–0.218 m³ (STP)/(m² h bar) with CO₂/CH₄ selectivity of 17.9–34.7 at different feed pressures up to 40 bar for a 10% CO₂ feed gas. Operating parameters of feed pressure, flow rate, and CO₂ concentration were found to significantly influence membrane performance. HYSYS simulation integrated with ChemBrane and cost estimation was conducted to evaluate techno‐economic feasibility of a membrane process for natural gas (NG) sweetening. Simulation results indicated that the developed FSC membranes could be a promising candidate for CO₂ removal from low CO₂ concentration (10%) NGs with a low NG sweetening cost of 5.73E?3 $/Nm³ sweet NG produced. © 2014 American Institute of Chemical Engineers AIChE J 60: 4174–4184, 2014     

Efficient capture of carbon dioxide with novel mass‐transfer intensification device using ionic liquids

A novel mass‐transfer intensified approach for CO₂ capture with ionic liquids (ILs) using rotating packed bed (RPB) reactor was presented. This new approach combined the advantages of RPB as a high mass‐transfer intensification device for viscous system and IL as a novel, environmentally benign CO₂ capture media with high thermal stability and extremely low volatility. Amino‐functionalized IL (2‐hydroxyethyl)‐trimethyl‐ammonium (S)?2‐pyrrolidinecarboxylic acid salt ([Choline][Pro]) was synthesized to perform experimental examination of CO₂ capture by chemical absorption. In RPB, it took only 0.2 s to reach 0.2 mol CO₂/mol IL at 293 K, indicating that RPB was kinetically favorable to absorption of CO₂ in IL because of its efficient mass‐transfer intensification. The effects of operation parameters on CO₂ removal efficiency and IL absorbent capacity were studied. In addition, a model based on penetration theory was proposed to explore the mechanism of gas–liquid mass transfer of ILs system in RPB. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2957–2965, 2013     

Modularization strategy for syngas generation in chemical looping methane reforming systems with CO2 as feedstock

This study considers a CO₂ feedstock in conventional methane reforming processes and metal oxide lattice oxygen based chemical looping reforming. Lattice oxygen from iron‐titanium composite metal oxide provides the most efficient co‐utilization of CO₂ with CH₄. A modularization chemical looping strategy is developed to further improve process efficiencies using a thermodynamic rationale. Modularization leverages the ability of two or more reactors operating in parallel to produce a higher quality syngas than a single reactor operating alone while offering a direct solution to scale up of multiple parallel reactor processes. Experiments conducted validate the thermodynamic simulation results. Simulation and experimental results ascertain that a cocurrent moving bed in a modularization system can operate under CO₂ neutral or negative conditions. The results for a modularization process system for 7950 m³ per day (50,000 barrels per day) of liquid fuel indicate a ～23% reduction of natural gas usage over baseline‐case. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3343–3360, 2017     

N‐doped porous carbons for CO2 capture: Rational choice of N‐containing polymer with high phenyl density as precursor

N‐doped porous carbons (NPCs) are highly promising for CO₂ capture, but their preparation is severely hindered by two factors, namely, the high cost of N‐containing polymer precursors and the low yield of carbon products. Here we report for the first time the fabrication of NPCs through the rational choice of the polymer NUT‐4, with low cost and high phenyl density, as precursor. For the material NPC‐600 obtained from carbonization at 600°C, the yield is as high as 52.1%. The adsorption capacity of CO₂ on NPC‐600 reaches 6.9 mmol/g at 273 K and 1 bar, which is obviously higher than that on the benchmarks, including 13X zeolite (4.1 mmol/g) and activated carbon (2.8 mmol/g), as well as most reported carbon materials. Our results also demonstrate that the present NPCs can be completely regenerated under mild conditions. The abundant microporosity and “CO₂‐philic” (N‐doped) sites are responsible for the adsorption performance. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1648–1658, 2017     

Hydrogen separation at elevated temperatures using metallic nickel hollow fiber membranes

Nickel is a cheaper metallic material compared to palladium membranes for H₂ separation. In this work, metallic Ni hollow fiber membranes were fabricated by a combined phase inversion and atmospheric sintering method. The morphology and membrane thickness of the hollow fibers was tuned by varying the spinning parameters like bore liquid flow rate and air gap distance. H₂ permeation through the Ni hollow fibers with N₂ as the sweep gas was measured under various operating conditions. A rigorous model considering temperature profiles was developed to fit the experimental data. The results show that the hydrogen permeation flux can be well described by using the Sieverts’ equation, implying that the membrane bulk diffusion is still the rate‐limiting step. The hydrogen separation rate in the Ni hollow fiber module can be improved by 4–8% when switching the co‐current flow to the countercurrent flow operation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3026–3034, 2017