Fabrication and characterization of silica modified polyimide–zeolite mixed matrix membranes for gas separation properties

The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes

Effects of novel silane modification of zeolite surface on polymer chain rigidification and partial pore blockage in polyethersulfone (PES)–zeolite A mixed matrix membranes

Mixed matrix membranes (MMMs) of polyimide (PI) and zeolite 13X, ZSM-5 and 4A were prepared by a solution-casting procedure. The effect of zeolite loading, pore size, and hydrophilicity/hydrophobicity of zeolite on the gas separation properties of these mixed matrix membranes were studied. Experimental results indicate that permeability of He, H2, CO2, and N2 increased with zeolite loadings. Selectivity of H2/N2 shows a slight improvement for low loadings of zeolites 13X and ZSM-5 but has a decreasing trend for zeolite 4A and high loadings of zeolites 13X and ZSM-5. In addition, selectivity of H2/CO2 remains low (1–3) while selectivity of CO2/N2 is significantly improved with the incorporation of the three zeolites in the polyimide membrane. Experimental permeabilities are higher than those predicted by the Maxwell model except for H2 and N2 permeabilities of the PI-4A system which are consistent with the predicted permeabilities. The proposed modified Maxwell model is capable of predicting the permeabilities of polyimide-zeolite 4A MMMs, but fails to simulate the permeability increase induced by interface voids in the polyimide-zeolite 13X and ZSM-5 systems.

In the current study, the effect of modified zeolite using (3-aminopropyl) triethoxysilane in polybutylene succinate (PBS) and polylactic acid (PLA) blend was investigated. Two types of modified zeolite i.e., zeolite 5A and 13X at 3wt% of polymer blend between PBS and PLA were mixed together in twin-screw extruder and thin-films were produced by cast-film extruder. The thickness of each film is between 50 – 70 micron. Mechanical properties, thermal properties, morphological properties and permeability of oxygen, carbon dioxide as well as water vapour were investigated. Adding of zeolite 5A into PBS/PLA blend was found to increase more tensile strength and Young’s moduluswith the comparison to zeolite 13X whereas the zeolite 13X and 5A had increased the percentage of elongation at break more than PBS/PLA blend. The zeolite 5A and 13X tended to increase the thermal stability of the composite films. Gas permeation results showed that PBS/PLA with zeolite 5A allowed the permeation of carbon dioxide and oxygen more than 13X in composite films. Moreover, water vapour transmissionrate of PBS/PLA with zeolite 5A was higher than the one with zeolite 13X.

The performance of zeolites 5A and 13X is numerically investigated in oxygen separation from air by a two-bed PSA system. The effect of operating variables such as adsorption step time, P H /P L ratio and cycle time was investigated on product purity and recovery. The simulation results showed that nitrogen adsorption capacity on zeolite 13X was slightly more than the one on zeolite 5A. In the completely same operating conditions, zeolite 5A had a larger mass transfer zone than zeolite 13X. Therefore, the adsorption and desorption rate of nitrogen on zeolite 5A is less than zeolite 13X. Moreover, for the equal volume of adsorbed nitrogen on both adsorbents, zeolite 5A is more capable rather than zeolite 13X to desorb much more volume of nitrogen at certain time. Furthermore, for achieving oxygen with purity of 96%, utilizing zeolite 5A is more economical than zeolite 13X, when 5.5<P H /P L <7 and 75<cycle time≤90.

In a way to overcome challenges with global warming, the use of fossil fuels in producing environmentally friendly energy towards reducing the ozone layer depletion and greenhouse gas emissions by participating countries is of interest. The adsorption refrigeration system has the advantages of a long lifespan and its environmental friendliness; however, its major disadvantage is the low coefficient of performance, which is a function of adsorbent–adsorbate, with zeolite–water as the most common adsorbent–adsorbate working pair. Zeolites 4A and 13X are the most used zeolite classes due to their higher selectivity for separating mixtures of CO2/N2 and CO2/CH4/N2 and their high-water adsorption capability, respectively. In this study, for the first time, the synthesis of zeolites 4A and 13X from natural sources (Kankara kaolin) and the mixture optimization for solar adsorption refrigeration application were considered. Raw Kankara kaolin, beneficiated Kankara kaolin, calcined Kankara kaolin and synthesized zeolites 4A and 13X were characterized using X-ray fluorescence, while the synthesized zeolites 4A and 13X were characterized using X-ray diffraction. Using the mixture simplex lattice design of experiment, mixtures of zeolites 4A and 13X were developed and characterized using Brunauer, Emmett and Teller analysis to obtain their pore size, specific surface area and pore volume. The statistical analysis produced the mathematical models of the response that were significant for pore size and specific surface area. The analysis proposed an optimal solution of 75 wt% zeolite 4A and 25 wt% zeolite 13X, which gave a desirability of 0.944.

Gas and water vapor transport properties of mixed matrix membranes containing 13X zeolite

Mixed matrix membranes prepared from poly(vinyl alcohol) (PVA) incorporated with zeolite 4A- graft-poly(2-hydroxyethyl methacrylate) (zeolite- g-PHEMA) for the pervaporation dehydration of water–acetone mixtures

The present research investigated the utilizing of single and dual-layer flat sheet mixed-matrix membranes (MMMs) for carbon dioxide (CO2) separation. In this research, zeolite 4A is incorporated into a processable polymeric material, polyethersulfone (PES) of MMMs to get the high selectivity and permeability of membrane. Single-layer flat sheet MMMs have been successfully fabricated by adjusting the weight percent of zeolite loading in total solid as the effect of zeolite loading on the performance of MMMs were investigated. It shows that the higher the zeolite loadings, the higher the CO2/CH4 selectivity which is from 1.54 at 0wt % zeolite loading to 3.20 at 20wt % zeolite loading. Besides that, dual-layer flat sheet MMMs was also successfully fabricated with blending of PES and zeolite as selective top-layer and neat PES as sub-layer. Comparison of the results of permeability and selectivity between single and dual layer MMMs with same zeolite loading were studied. The performance of these newly developed dual-layer flat sheet of MMMs gives the best result with CO2/CH4 selectivity for dual layer MMMs is 9.63, tripled of the selectivity of single layer MMMs, 3.20.

Adsorptive removal of ultra-low concentration H2S and THT in CH4 with and without CO2 on zeolite 5A and 13X pellets

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

The present study aimed to investigate the adsorption behavior of heavy metal ions (Cu 2+ , Cd 2+ , and Pb 2+ ) on zeolite 4A (26.9 m 2 /g) and zeolite 13X (550.1 m 2 /g) at neutral pH in batch experiments. Influencing parameters on the adsorption were studied, including equilibrium time, solution pH, and adsorbent dose. The metal removal efficiencies at neutral pH were considerably higher than those at acidic pH. Cu 2+ and Cd 2+ were more efficiently adsorbed on zeolite 4A, while the greater removal of Pb 2+ was achieved with zeolite 13X. With an initial concentration of 300 ppm and an adsorbent‐to‐liquid ratio of 0.2% w/v, the highest removal efficiencies were 91.1% for Cu 2+ and 95.2% for Cd 2+ with zeolite 4A, and 92.9% for Pb 2+ with zeolite 13X. The experimental data fitted well with the Langmuir isotherm and the pseudo‐second‐order models, indicating the monolayer formations and the dominance of chemisorption. Zeolite 4A showed higher pseudo‐second‐order rate constants than zeolite 13X. The intraparticle diffusion contributed more significantly to the adsorption of Cu 2+ and Cd 2+ than that of Pb 2+ on the zeolites. The findings from this study provide valuable insights into the adsorption behavior of heavy metals on different kinds of zeolites in neutral solution.

Zeolite filled P84 co-polyimide membranes for dehydration of isopropanol through pervaporation process

The effects of the impregnation of three types of inorganic fillers into polyvinylidene fluoride (PVDF) polymer membranes on the gas permeability and selectivity of these membranes were studied theoretically and experimentally. Permeabilities of He, CO2, O2, and N2 through three types of mixed matrix membranes (MMMs) based on PVDF, that is, PVDF/SiO2, PVDF/MCM‐41, and PVDF/4A MMMs, were experimentally measured and theoretically predicted using Maxwell, Higuchi, Bruggeman, and Bottcher‐Landauer models. Theoretical permeabilities of the PVDF/SiO2 MMMs using the above four models predicted the results in the following order: Maxwell model&gt;Bruggeman model&gt;Bottcher model&gt;Higuchi model. However, this sequence was reversed for PVDF/MCM‐41 MMMs. The nonporous SiO2, mesoporous MCM‐41 and zeolite 4A inorganic fillers had effects on the permeabilities of the challenge gases for the PVDF/SiO2, PVDF/MCM‐41, and PVDF/4A MMMs but had no effects on the selectivities of the MMMs. The experimental permeabilities of the MMMs showed that there were no significant differences among the three types of MMMs despite that the inorganic fillers, that is, SiO2, MCM‐41, and zeolite 4A, had distinct dissimilar properties such as pore structures and particle sizes. Density measurements indicated that some voids were present in the polymer/particle interfaces. Based on the density measurement results, the void volume fractions of the resulting MMMs were calculated. An equation is derived to determine the void thickness of the MMM in terms of its physical properties and hence this proposed equation can substitute the difficult task of measuring such void thickness through any microscopy techniques. The Maxwell, Higuchi, Bruggeman, and Bottcher‐Landauer models could not predict the actual gas permeabilities of the PVDF MMMs. By taking the effects of crystallinity and immobilization factor on gas permeability into consideration, the extended modified Maxwell model showed good agreement with the experimental gas permeabilities of the resulting MMMs, indicating that the model did capture the essence of the gas transport behaviors through the MMMs. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4715–4726, 2013

ABSTRACTThe effect of zeolite 3A, 4A, and ZSM‐5 on the gas separation performance of polyurethane (PU)–zeolite mixed matrix membranes (MMMs) has been investigated in this study. Permeation of pure CO2, CH4, N2, and O2 gases through PU–zeolite MMMs with zeolite content of 6, 12, 18, and 24 wt% was studied. The prepared hybrid membranes were characterized using Fourier transform infrared spectroscopy and scanning electron microscope. Membrane characterization confirmed the homogeneous distribution of zeolite particles at low zeolite loadings in the prepared membranes. The obtained results confirmed a significant enhancement in the permeability of all gases and the CO2/N2, CO2/CH4, and O2/N2 selectivities by increasing the content of zeolite particles in PU–zeolite MMMs. The PU–zeolite 4A with 12 wt% zeolite loading showed the best performance in terms of gas permeability and selectivity for CO2/N2, CO2/CH4 and O2/N2 gas pairs.