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.     

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.     

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.     

GNs/MOF-based mixed matrix membranes for gas separations

NU-1000 and graphene nanosheet (GNs) with different loadings have been used as fillers to prepare mixed matrix membranes (MMMs) with polyethersulfone (PES). The high performance of the MMMs has been successfully fabricated for the evaluation of gas separation at 1 bar and various temperatures (20, 40, 60 °C). The successful fabrication of the MMMs were confirmed by using SEM, FTIR, AFM, and XRD. The crystalline nature of GNs and NU-1000 in the MMMs are evidenced by XRD, which confirms the successful fabrication of the MMMs. In addition, the thermal stability of the MMMs was enhanced with the increase of the GNs. Separation performance of H₂ was superior to CO₂, N₂ and CH₄ separation on the MMMs which is a critical for producing energy. The best gas separation results in terms of both permeability and selectivity were obtained with 0.03% GNs and 10% NU-1000. PG3N membrane presented maximum H₂/CO₂, H₂/N₂ and H₂/CH₄ selectivity of 5, 4.2, 3.3 at 20 C, respectively. With an increase in temperature, the permeability increased, while the selectivity of all the MMMs decreased. The MMMs exhibited excellent gas separation capability, which offers unique opportunities for potential large-scale practical applications.     

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.     

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.     

Hydrogen separation and purification with poly (4-methyl-1-pentyne)/MIL 53 mixed matrix membrane based on reverse selectivity

The effect of MIL 53 (Al) metal organic framework on gas transport properties of poly (4-methyl-1-pentyne) (PMP) was determined based on reverse selectivity. Mixed matrix membranes (MMMs) were fabricated considering various weight percent of MIL 53 particles. The reverse MMMs permselectivities were evaluated through measurement of pure CO₂ and H₂ permeation together with calculation of CO₂/H₂ selectivity. The PMP/MIL 53 (Al) MMMs exhibited privileged CO₂/H₂ permselectivity in comparison with the neat PMP. In addition, CO₂ solubility coefficient was significantly increased with increasing the MIL 53 loading, while the H₂ solubility coefficient was almost remained unchanged. Moreover with increasing the feed pressure the permeability of CO₂ and CO₂/H₂ selectivity were dramatically enhanced, especially at higher filler loadings. Therefore, it was observed that the reverse selectivity of MMMs was enhanced so that the Robeson upper bound was overcome. The best yielding membranes (PMP/30 wt.% MIL 53) represented the CO₂ permeability and CO₂/H₂ selectivity of 377.24 barrer and 24.91 for pure gas experiments 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.     

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.     

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.     

H2 permeation and its influence on gases through a SAPO-34 zeolite membrane

This work analysed the permeation of binary and ternary H₂-containing mixtures through a SAPO-34 membrane, aiming at investigating how hydrogen influences and its permeation is influenced by the presence of the other gaseous species, such as CO₂ and CH₄. We considered the behaviour of various gas mixtures in terms of permeability and selectivity at various temperatures (25–300 °C), feed pressures (400–1000 kPa) and compositions by means of an already validated mass transport model, which is based on surface and gas translation diffusion. We found that the presence of CO₂ and CH₄ in the H₂-containing mixtures influences in a similar way the H₂ permeation, reducing its permeability of about 80% compared to the single-gas value because of their stronger adsorption. On the other hand, H₂ promotes the permeation of CO₂ and CH₄, causing an increment of their permeability with respect to those as single gases. These combined effects reflected in interesting selectivity values in binary mixture (e.g., CO₂/H₂ about 11 at 25 °C, H₂/CH₄ about 9 at 180 °C), which showed the potential of SAPO-34 membranes in treating of H₂-containing mixtures.     

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.     

Hydrogen and synthesis gas co-production on oxygen membranes of mixed conductor: Scale-sensitive features of the process

The tubular ceramic membrane of La_0.5Sr_0.5FeO_3–δ was tested in a condition of simultaneous partial oxidation of methane (POM), occurring in space adjacent to the outer surface of the membrane, and water splitting (WS) accompanied by hydrogen generation taking place in the internal membrane space. It was shown that a membrane with a surface area of more than 10 cm² could successfully operate without carrier gases. A detected effect of CO selectivity in POM on the thermal condition of the process was another result using a membrane of notable size. The heat power released/absorbed on the membrane, associated with partial oxidation of methane and water splitting, was calculated using experimental data. The absorbed heat power of the overall process was found to be sensitive to CO selectivity, especially if selectivity exceeded 80%. The combined POM and WS process with the hydrogen production rate of ∼2 mL min⁻¹cm⁻² during 300 h with stable methane conversion of about 99% and CO selectivity around 96% was successfully carried out.     

Effect of zeolites on chitosan/zeolite hybrid membranes for direct methanol fuel cell

Zeolites including 3A, 4A, 5A, 13X, mordenite, and HZSM-5 were incorporated into chitosan (CS) matrix to fabricate the hybrid membranes for direct methanol fuel cell (DMFC). Due to the presence of hydrogen bonds between CS and zeolite, the hybrid membranes displayed desirable thermal and mechanical stabilities. Through free volume characteristics analysis by positron annihilation lifetime spectroscopy (PALS) technique, it was found that incorporation of hydrophilic zeolites would increase the free volume cavity size whereas incorporation of hydrophobic zeolites would decrease the free volume cavity size. Through the investigations on water/methanol uptake, swelling, and methanol permeability, it was found that the membrane performance was highly dependent on the zeolite particle and pore size, content, and hydrophilic/hydrophobic nature. Based on the solution–diffusion mechanism, it was found that incorporation of hydrophobic zeolites increased the diffusion resistance of methanol and consequently decreased the methanol permeability, whereas incorporation of hydrophilic zeolites decreased the diffusion resistance of methanol and consequently increased the methanol permeability. Moreover, under the identical conditions, all the as-prepared membranes exhibited much lower methanol permeability than Nafion^® 117 while the proton conductivity of the membranes remained high enough for DMFC applications.     

H2-selective mixed matrix membranes modeling using ANFIS,PSO-ANFIS,GA-ANFIS

The novel contribution of the current study is to employ adaptive neuro-fuzzy inference system (ANFIS) for evaluation of H₂-selective mixed matrix membranes (MMMs) performance in various operational conditions. Initially, MMMs were prepared by incorporating zeolite 4A nanoparticles into polydimethylsiloxane (PDMS) and applied in gas permeation measurement. The gas permeability of CH₄, CO₂, C₃H₈ and H₂ was used for ANFIS modeling. In this manner, the H₂/gas selectivity as the output of the model was modeled to the variations of feed pressure, nanofiller contents and the kind of gas, which were defined as input (design) variables. The proposed method is based on the improvement of ANFIS with genetic algorithm (GA) and particle swarm optimization (PSO). The PSO and GA were applied to improve the ANFIS performance. To determine the efficiency of PSO-ANFIS, GA-ANFIS and ANFIS models, a statistical analysis was performed. The results revealed that the PSO-ANFIS model yields better prediction in comparison to two other methods so that root mean square error (RMSE) and coefficient of determination (R²) were obtained as 0.0135 and 0.9938, respectively. The RMSE and R² values for GA-ANFIS were 0.0320 and 0.9653, respectively, and for ANFIS model were 0.0256 and 0.9787, respectively.     

Deposition of an ultrathin palladium (Pd) coating on SAPO-34 membranes for enhanced H2/N2 separation

Hydrogen energy has attracted great attention due to its properties of high energy transferring efficiency and zero pollution emission. Zeolite membranes are promising candidates for H₂ separation because of their uniform, molecular-sized pores and high thermal and mechanical stabilities. However, thicker membranes or modification treatments are often necessary to eliminate the defects formed during synthesis and post calcination, leading to low gas permeance. Herein, we reported the deposition of an ultrathin palladium (Pd) coating on SAPO-34 membranes to improve H₂ separation performance. H₂/N₂ selectivity was greatly increased by deposition of an ultrathin Pd coating on SAPO-34 membranes, while maintaining similar H₂ permeance. This might be attributed to the dissociative adsorption and associative desorption of H₂ on Pd, as well as fast diffusion of H₂ through ultrathin Pd coating. We also noticed that excessive Pd deposition would lead to the formation of cracks on SAPO-34 membranes, leading to deteriorated membrane performance.     

Hydrogen separation performance of CMS membranes derived from the imide-functional group of two similar types of precursors

Carbon molecular sieve (CMS) membranes derived from polyimide (PI) and polyetherimide (PEI), which have similar functional groups were fabricated for gas separation. To evaluate the effect of the functional groups of PI and PEI on the properties of their CMS membranes, the composition of the casting solution and carbonization temperatures were investigated. Thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FE-SEM) were employed to characterize thermal stability, functional groups and microstructural change in the derived CMS membrane. The gas permeation performance of the CMS membranes were estimated using four gases: hydrogen, carbon dioxide, nitrogen and methane. The results show that CC stretching in imides exhibit an intense absorption peak at 1665 cm⁻¹ with PI dominating the insignificant degradation of the imide groups at the intermediate stage. For PEI, the absorption peaks of CN stretching and C-C-C bending were intense at 1011 and 1068 cm⁻¹ respectively, dominating the ethers and cyclic ethers of asymmetric stretching. The microstructure and gas permeation properties of the obtained CMS membranes were significantly affected by the functional group of precursors and their concentrations in the casting solution. Optimized performance for hydrogen permeation (565 Barrer) [1 Barrer = 1 × 10⁻¹⁰ cm³ (STP) cm/(cm² s cmHg)] was obtained with PI-10-600 CMS membrane. The best selectivity for H₂/N₂ at 33.2 was obtained from PI-10-500 CMS membrane.     

Hydrogen separation through the use of mixed oxygen ion and electron conducting membranes (I): theoretical analysis

Membrane-based processes are becoming increasingly important in the field of industrial gas separation. Such processes are attractive from the standpoint of high separation selectivity and high conversion ratios in cases involving gas phase and gas–solid reactions. In particular, the application of dense ceramic mixed ionic and electronic conducting membranes to separate gases such as oxygen through ambipolar transport of oxygen ions and electrons and hydrogen through ambipolar transport of protons and electrons from gas mixtures at elevated temperatures (>500°C) is gaining increasing importance. As a specific example, the requirement of high-purity tonnage hydrogen with less than 10 ppm carbon monoxide impurity levels would be absolutely essential for low-temperature proton exchange membrane fuel cells to gain wide market acceptance. We analyze herein a novel membrane-based hydrogen separation process which has heretofore not been widely reported in the literature.     

Hydrogen separation and stability study of ceramic membranes based on the system Nd5LnWO12

This contribution presents the preparation, permeation and stability study of mixed protonic-electronic conducting membranes based on the system Nd₅LnWO₁₂. The tungstates Ln₆WO₁₂ are proton conducting crystalline materials, which show sufficient protonic and electronic mixed conductivity and stability in moist CO₂ environments to consider them as potential candidates for the separation of hydrogen at high temperatures. Hydrogen separation properties of A-substoichiometric Nd₆WO₁₂ and Nd₅LaWO₁₂ were systematically analyzed, i.e. the influence of the H₂ concentration in feed stream, humidification degree and operating temperature on the hydrogen separation was studied. Finally, the stability of these materials at different temperatures and CO₂-rich and sulfur-containing environments was evaluated.