Hydrogen separation and purification using crosslinkable PDMS/zeolite A nanoparticles mixed matrix membranes

The transport properties of gases in polydimethylsiloxane (PDMS)/zeolite A mixed matrix membranes (MMMs) were determined based on pure gas permeation experiments. MMMs were prepared by incorporating zeolite 4A nanoparticles into a PDMS matrix using a new procedure. The permeation rates of C₃H₈, CH₄, CO₂, and H₂ were evaluated through a dense homogeneous pure PDMS membrane and PDMS/4A MMMs to assess the viability of these membranes for natural gas sweetening and hydrogen purification. SEM investigations showed good adhesion of the polymer to the zeolite in MMMs. Permeation performance of the membranes was also investigated using a laboratory-scale gas separation apparatus and effects of feed pressure, zeolite loading and pore size of zeolite on the gas separation performance of the MMMs were evaluated. The MMMs exhibited both higher selectivity of H₂/CH₄ and H₂ permeability as compared with the neat PDMS membrane, suggesting that these membranes are very promising for gas separations such as H₂/CH₄ separation.     

Gas permeation through H2-selective mixed matrix membranes: Experimental and neural network modeling

Gas permeability through synthesized polydimethylsiloxane (PDMS)/zeolite 4A mixed matrix membranes (MMMs) were investigated with the aid of artificial neural network (ANN) approach. Kinetic diameter and critical temperature of permeating components (e.g. H₂, CH₄, CO₂ and C₃H₈), zeolite content and upstream pressure as input variables and gas permeability as output were inspected. Collected data of the experimental operation was used to ANN training and optimum numbers of hidden layers and neurons were obtained by trial-error method. The selected ANN architecture (4:10:1) was used to predict gas permeability for different inputs in the domain of training data. Based on the results, the predicted values demonstrate an excellent agreement with the experimental data, with high correlation (R² = 0.9944) and less error (RMSE = 1.33E−4). Furthermore, using sensitivity analysis, kinetic diameter and critical temperature were found as the most significant effective variables on gas permeability. As a result, ANN can be recommended for the modeling of gas transport through MMMs.     

Experimental investigation of natural polysaccharide-based mixed matrix membrane modified with graphene oxide and Pd-nanoparticles for enhanced gas separation performance

In this work, we proposed a mixed matrix membrane prepared by using a glycerol modified guar gum (GGP) polymer matrix incorporated with graphene oxide (GO). The influence of varying GO concentration on the gas separation performance was investigated and 2 wt% was found to be the optimum concentration for high performance. The 2 wt% GO mixed matrix membranes were further modified with Pd nanoparticles. When GO, and Pd nanoparticles were mixed, CO₂ permeability increased by 49.94%, while the permeability of H₂ gas molecules decreased by 98.11%, respectively, compared to the pristine GGP membrane. The selectivity of CO₂/H₂ was obtained as 18.27. The glass transition temperature of the membrane increased from 85 to 95.2 °C, tensile strength and elongation of the break were significantly improved by 29.09% and 84.37% through the addition of Pd and GO into the membrane. The scanning electron microscopy revealed a dense top surface after GO nanosheets incorporation. Further, the thermogravimetric analysis proposes that the modified membrane is thermally stable than GGP. Henceforth, the study suggests GO incorporation and Pd nanoparticles modification of guar gum membrane is a promising gas separation membrane with potentially high selectivity for CO₂ gas.     

Gas sorption in H2-selective mixed matrix membranes: Experimental and neural network modeling

Robust artificial neural network (ANN) was developed to forecast sorption of gases in membranes comprised of porous nanoparticles dispersed homogenously within polymer matrix. The main purpose of this study was to predict sorption of light gases (H₂, CH₄, CO₂) within mixed matrix membranes (MMMs) as function of critical temperature, nanoparticles loading and upstream pressure. Collected data were distributed into three portions of training (70%), validation (19%), and testing (11%). The optimum network structure was determined by trial-error method (4:6:2:1) and was applied for modeling the gas sorption. The prediction results were remarkably agreed with the experimental data with MSE of 0.00005 and correlation coefficient of 0.9994.     

Structure-controlled mesoporous SBA-15-derived mixed matrix membranes for H2 purification and CO2 capture

The composite mixed matrix membranes (MMMs) were prepared by incorporating mesopore SBA-15 as a filler to discuss the effects of its particle shape, particle size, and loadings on the organic–inorganic interfacial morphology. The SBA-15 was synthesized by template method and it's particle shape and size was adjusted by adding electrolyte. The results indicated that the spherical SBA-15 can improve the dispersion and have better adhesion with organic phase, which showed better permselectivity than the rod-like one. The SBA-15 filler also could increase the diffusion selectivity of MMMs by the addition of different particle sizes. The permeabilities of H₂ and CO₂ were 1207.9 and 552.86 Barrer, respectively, with selectivities of H₂/CH₄ and CO₂/CH₄ reached 247.0 and 112.8, respectively, when 1.6 μm spherical SBA-15 was added at 3 wt. %. The dissimilarity occurring in the perm-selectivity values with changes made in the particle shape and size are much more pronounced at the lower SBA-15 loading, which exceeded the 2008 Robeson's upper bound limited.     

Fabrication and characterization of poly(phenylene oxide)/SBA-15/carbon molecule sieve multilayer mixed matrix membrane for gas separation

A novel multilayer mixed matrix membrane (MMM), consisting of poly(phenylene oxide) (PPO), large-pore mesoporous silica molecular sieve zeolite SBA-15, and a carbon molecular sieve (CMS)/Al₂O₃ substrate, was successfully fabricated using the procedure outlined in this paper. The membranes were cast by spin coating and exposed to different gases for the purpose of determining and comparing the permeability and selectivity of PPO/SBA-15 membranes to H₂, CO₂, N₂, and CH₄. PPO/SBA-15/CMS/Al₂O₃ MMMs with different loading weights of zeolite SBA-15 were also studied. This new class of PPO/SBA-15/CMS/Al₂O₃ multilayer MMMs showed higher levels of gas permeability compared to PPO/SBA-15 membranes. The permselectivity of H₂/N₂ and H₂/CH₄ combinations increased remarkably, with values at 38.9 and 50.9, respectively, at 10 wt% zeolite loading. Field emission scanning electron microscopy results showed that the interface between the polymer and the zeolite in MMMs was better at a 10 wt% loading than other loading levels. The increments of the glass transition temperature of MMMs with zeolite confirm that zeolite causes polymer chains to become rigid.     

Sorption properties of hydrogen-selective PDMS/zeolite 4A mixed matrix membrane

The present study explores the fundamental science of estimating sorption of gases in membranes comprised of inorganic porous fillers within a polymer matrix with a novel semi-empirical correlation. The sorption properties of H₂, C₃H₈, CO₂ and CH₄ were determined in polydimethylsiloxane (PDMS)/zeolite 4A mixed matrix membranes (MMMs) to assess the viability of these membranes for hydrogen purification and natural gas sweetening. Zeolite filling in MMMs results an increase in solubility over neat PDMS membrane. In addition, incorporation of zeolite 4A to PDMS membrane improved H₂ permeation and H₂/CH₄ selectivity. The results confirmed that zeolite 4A can significantly improve the separation properties of poorly H₂-selective PDMS membrane from 0.7 up to 11 and this overcomes the Robeson upper-bound limitation. This improvement was explained referring the Flory–Huggins interaction parameter within MMMs.     

Recent advances in the development of supported carbon membranes for gas separation

Carbon membranes have emerged in the 70's and have been presenting promising results for application in processes involving gas separation because of their sieving effects. The carbon membranes are obtained by pyrolysis of a precursor polymer beyond its initial decomposition temperature under essentially inert conditions. Supported and unsupported carbon membranes can be produced, but the former are distinguished for the industrial separation of gases due to the improved mechanical strength and high chemical and thermal stability. In this context, different types of support, coating methods and pyrolysis conditions for supported carbon membranes have been reported in the literature, in order to improve the separation capability of gas mixtures in respect to permeability and selectivity. The aim of this review article is to report and discuss the evolution of supported carbon membrane in the last 10 years in respect to configuration, transport mechanisms, manufacturing processes and its main applications, highlighting the main challenges still to be overcome for this technology to be applied industrially.     

ZnO nanofiber skeleton induced robust zeolitic imidazolate framework membranes for gas separation

Rationally designing compact metal-organic framework (MOF) membrane is highly desired but challenging. Herein, we proposed a ZnO nanofiber skeleton induced zeolitic imidazolate framework (ZIF) membrane inspired by the reinforced concrete structure. In this process, the ZnO nanofiber skeleton was employed as active anchor sites to assist the heteroepitaxial growth of continuous membranes, like the reinforcing steel in structure. The formed ZIFs particles were tightly embedded in the skeleton like the concrete. With this approach, highly compact Co-based ZIF-9 membrane and Zn-based ZIF-8 membrane were successfully achieved and exhibit effective H₂ separation performance. For ZIF-9 membrane, the H₂ permeance and the ideal selectivity of H₂/CO₂ are 2.19 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ and 15.3, respectively. For ZIF-8 membrane, the H₂ permeance and the ideal selectivity of H₂/CH₄ are 2.26 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 9.7, respectively. More importantly, benefiting from the novel structure, the membrane showed a highly robust architecture under different pressures, good durability against rubbing, and separation stability of 100 h. This strategy provides a new approach toward other compact and robust MOF membrane.     

Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H2/CO2 separations

Thermally robust membranes are required for H₂ production and carbon capture from hydrocarbon fuel derived synthesis (syn) gas. Polybenzimidaole (PBI) materials have exceptional thermal, chemical and mechanical characteristics and high H₂ perm-selectivity for efficient syngas separations at process relevant conditions. The large gas volumes processed mandate the use of a high-throughput, small footprint hollow fiber membrane (HFM) platform. In this work, an industrially attractive spinning protocol is developed to fabricate PBI HFMs with unprecedented H₂/CO₂ separation performance. A unique dope composition incorporating an acetonitrile diluent is discovered enabling asymmetric macro-void free PBI HFM fabrication using a water coagulant. The influences of dope viscosity, coagulant chemistry, and air gap on HFM morphology are evaluated. Elevated temperature (up to 350 °C) H₂ permeances of 400 GPU with H₂/CO₂ selectivities > 20 are achieved. This unprecedented separation performance is a ground breaking achievement at temperatures traditionally considered out-of-reach for polymeric membranes.     

Selective storage and evolution of hydrogen on nafion/NaCl/graphene quantum dot mixed matrix using tensammetry as power electrochemical technique

Hydrogen storage/evolution behavior of nafion/NaCl/graphene quantum dot (GQD) mixed matrix as selective hydrogen capacitor (power source) was evaluated in detail through an electrochemical process at two independent potential ranges. For this purpose, a three-electrode system included Pt disk as counter electrode, Ag/AgCl as reference electrode and GQD-based mixed matrix-modified Pt disk as working electrode. For hydrogen storage, the deposition potential and time were evaluated to ?1.0 V (vs. Ag/AgCl) and 120 s, respectively under high basic solution generated using NaOH (1.0 M) solution, followed by evolution of hydrogen at +0.8 V (vs. Ag/AgCl) during formation of hydrogen bubbles. The main advantage of this system was the occurrence of hydrogen storage and evolution at two independent potential windows. Both mass transfer and adsorption processes were estimated for the tensammetric peak during the evolution step. The mechanism of hydrogen storage and evolution was obeyed from diffusion and tensammetry, respectively. According to Randles–Sevcik equation using 1.0 mM ${{\text{Fe}\left(\text{CN}\right)}_6}^{3?/4?}$, the active surface area of nafion/NaCl/GQD mixed matrix was ～1906 m²g^?1. Based on the CHN analyses, pressure-concentration temperature as well as hydrogen temperature-programmed desorption, the capacity of the synthesized GQDs for hydrogen storage and evolution was estimated to at least 10.1 and 8.6 wt%, respectively. The stability of the electrode was also estimated during 7000s by chronoamperometry during applying at least 40 cycles in the range from ?1.0 to +1.3 V with reproducible tensammetric peak current (relative standard deviation: 2.54%).     

Hydrogen gas separation with controlled selectivity via efficient and cost effective block copolymer coated PET membranes

An efficient way is suggested to reduce the cost of block copolymer (BC) membranes while still taking advantage of their unique properties. It is demonstrated that selectivity can be kept almost the same whereas permeability is varied by using thin copolymer films on robust porous PET polymer membranes which acts as a mechanical support. So, a nanoscopic thin selective layer of the block copolymer (PS-b-P4VP) with additive is casted on the PET porous support. Selective extraction of the additive from the block copolymer thin films leads to the formation of a layer with monodispersed pores on the PET support. Measurements of the gas permeability of PET membranes of different pore size with and without block copolymer coating reveal that permeabilities of BC coated membranes decrease whereas selectivities slightly increase in comparison to the porous PET support. Coating of the membranes with BC plays a valuable role for the selectivity against gases like H₂ over CO₂. The surface morphology of the composite membranes has been determined by atomic force microscopy (AFM) showing the nanoscopic pores. Due to excellent mechanical stability and easy scale up, such membranes may be used in the gas separation technology.     

Development of hybrid models for prediction of gas permeation through FS/POSS/PDMS nanocomposite membranes

The present paper aims to use intelligent methods for prediction of gas permeation in binary-filler nanocomposite membranes containing fumed silica (FS) and octatrimethylsiloxy polyhedral oligomeric silsesquioxane (POSS) nanoparticles incorporated within a polymer matrix of polydimethylsiloxane (PDMS). Two reliable and rigorous hybrid models, i.e., differential evolution-adaptive neuro-fuzzy inference system (DE-ANFIS) and coupled simulated annealing-least square support vector machine (CSA-LSSVM) were developed in order to predict pure gas permeability of including H₂, CH₄, CO_2, and C₃H₈ through the nanocomposite membranes. The coupled simulated annealing (CSA) optimization algorithm was also used for tuning of the model parameters. The impacts of several key parameters such as pressure, FS nanoparticles loading as well as the kinetic diameter of gases on permeation were investigated. The experimental data were randomly divided into two main groups, namely training (70%) and testing (30%) sets. The results of the study suggested that DE-ANFIS model is a more robust and accurate model than the CSA-LSSVM with the R² values of 0.9981 and 0.9689, respectively.     

Preparation of mixed matrix composite membrane for hydrogen purification by incorporating ZIF-8 nanoparticles modified with tannic acid

The incompatibility between nanofillers and polymer, caused by the agglomeration of nanoparticles and their weak interaction with each other, is still a challenge to develop mixed matrix composite membrane. Herein, we introduced the ZIF-8-TA nanoparticles synthesized by in situ hydrophilic modification into the hydrophilic poly(vinylamine) (PVAm) matrix to prepare composite membranes for H₂ purification. The dispersion of ZIF-8 in water was improved by tannic acid modification, and the compatibility between ZIF-8 particles and PVAm matrix was enhanced by chemical crosslinking between the quinone groups in oxidized tannic acid (TA) and the amino groups in PVAm. Moreover, the compatibility between hydrophobic polydimethylsiloxane (PDMS) gutter layer and hydrophilic separation layer was achieved by the adhesion of TA-Fe³⁺ complex to the surface of PDMS layer during membrane preparation. The interlayer hydrophilic modification and the formation of separation layer were accomplished in one step, which simplified the preparation process. The experimental results indicated that when the TA addition used for modification was 0.5 g and the ZIF-8-TA_0.5 content in membrane was 12 wt%, the prepared membrane showed the best separation performance with the CO₂ permeance of 987 GPU and the CO₂/H₂ selectivity of 31, under the feed gas pressure of 0.12 MPa.     

Metal-organic framework MIL-101(Cr) based mixed matrix membranes for esterification of ethanol and acetic acid in a membrane reactor

Mixed matrix membranes (MMMs) based on the polyimide Matrimid^® (PI) with metal-organic framework (MOF) MIL-101(Cr) as porous nanostructured filler were synthesized and applied as separation element in a membrane reactor to carry out the esterification of acetic acid with ethanol. The MMMs were characterized by techniques including X-ray diffraction, IR spectroscopy and scanning electron microscopy. In order to compare the performance of MIL-101(Cr)-PI MMMs in the membrane reactor, pure PI and HKUST-1-PI membranes were also used. MMMs provided a better reactor performance than the bare PI membrane because of the increase in permeability associated to the presence of MOF as filler. The PI membrane reactor barely achieved the same conversion as a fixed bed reactor, while the MIL-101(Cr)-PI membrane showed a reactor performance similar to that of the HKUST-1-PI membrane with higher stability, as confirmed by membrane characterization after the reaction experiments.     

High performance composite hollow fiber membranes for CO2/H2 and CO2/N2 separation

The search for a clean energy source as well as the reduction of CO₂ emissions to the atmosphere are important strategies to resolve the current energy shortage and global warming issues. We have demonstrated, for the first time, a Pebax/poly(dimethylsiloxane)/polyacrylonitrile (Pebax/PDMS/PAN) composite hollow fiber membrane not only can be used for flue gas treatment but also for hydrogen purification. The composite membranes display attractive gas separation performance with a CO₂ permeance of 481.5 GPU, CO₂/H₂ and CO₂/N₂ selectivity of 8.1 and 42.0, respectively. Minimizing the solution intrusion using the PDMS gutter layer is the key to achieving the high gas permeance while the interaction between poly(ethylene oxide) (PEO) and CO₂ accounts for the high selectivity. Effects of coating solution concentration and coating time on gas separation performance have been investigated and the results have been optimized. To the best of our knowledge, this is the first polymeric composite hollow fiber membrane for hydrogen purification. The attractive gas separation performance of the newly developed membranes may indicate good potential for industrial applications.     

CO2-selective membranes for hydrogen purification and the effect of carbon monoxide (CO) on its gas separation performance

Industrial hydrogen production may prefer CO₂-selective membranes because high-pressure H₂ can therefore be produced without additional recompression. In this study, high performance CO₂-selective membranes are fabricated by modifying a polymer–silica hybrid matrix (PSHM) with a low molecular weight poly(ethylene glycol) dimethyl ether (PEGDME). The liquid state of PEGDME and its unique end groups eliminate the crystallization tendency of poly(ethylene glycol) (PEG). The methyl end groups in PEGDME hinder hydrogen bonding between the polymer chains and significantly enhance the gas diffusivity. In pure gas tests, the membrane containing 50 wt% additive shows CO₂ gas permeability and CO₂/H₂ selectivity of 1637 Barrers and 13 at 35 °C, respectively. In order to explore the effect of real industrial conditions, the gas separation performance of the newly developed membranes has been studied extensively using binary (CO₂/H₂) and ternary gas mixtures (CO₂/H₂/carbon monoxide (CO)). Compared to pure gas performance, the second component (H₂) in the binary mixed gas test reduces the CO₂ permeability. The presence of CO in the feed gas stream decreases both CO₂ and H₂ permeability as well as CO₂/H₂ selectivity as it reduces the concentration of CO₂ molecules in the polymer matrix. The mixed gas results affirm the promising applications of the newly developed membranes for H₂ purification.     

A novel strategy for surface modification of polyimide membranes by vapor-phase ethylenediamine (EDA) for hydrogen purification

In this study, vapor-phase ethylenediamine (EDA) is utilized to specifically modify the physicochemical properties of the outer surface of polyimide membranes without modifying the internal membrane structure for hydrogen purification. The surfaces of polyimide membranes before and after EDA-vapor modification have been characterized by Fourier transform infrared-attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), which confirmed the modification mechanism including the conversion of imide groups into amide groups with simultaneous cross-linking between polymer chains and a physical decrement in d-space. Based on pure gas permeation tests, only a 10-min vapor-phase EDA treatment can significantly improve H₂/CO₂ selectivity (up to ∼100). This is attributed to intensive surface modification by EDA vapor, hence rendering this simple and yet novel technique more effectively for hydrogen purification than the conventional solution approach. Although the H₂/CO₂ separation performance in mixed gas tests is not as superior as that in pure gas permeation tests, mixed gas results affirmed impressive H₂/CO₂ separation performance of vapor-phase EDA modified polyimide membranes. This novel vapor modification strategy appears to be promising for large-scale processes, especially the modification of hollow fiber membranes for industrial hydrogen purification.     

Dual gas sensing properties of graphene-Pd/SnO2 composites for H2 and ethanol: Role of nanoparticles-graphene interface

In the present work, role of palladium (Pd) and tin oxide (SnO₂) nanoparticles (NPs) deposited on graphene has been investigated in terms of dual gas sensing characteristics of ethanol and H₂ between two temperatures. The incorporation of nanoparticles into graphene has been observed which results a large change in the sensing response towards these gases. It is investigated that, incorporation of isolated Pd NPs on the graphene facilitates the room temperature sensing of H₂ gas with fast response and recovery time whereas, isolated SnO₂ NPs on graphene enables the detection of ethanol at 200 °C. However, combination of isolated Pd and SnO₂ NPs on graphene shows improved sensitivity and good selectivity towards H₂ and ethanol, usually not observed in chemiresistive gas sensors. Catalytic PdH interaction and corresponding change in work function of nanoparticles on hydrogenation resulting in modifications in electronic exchange between Pd, SnO₂ and graphene are responsible for the observed behavior. These results are important for developing a new class of chemiresistive type gas sensor based on change in the electronic properties of the graphene and NPs interfaces.