Project description:Due to their interfacial defects between inorganic fillers and polymer matrices, research into mixed matrix membranes (MMMs) is challenging. In the application of CO2 separation, these defects can potentially jeopardize the performance of membranes. In this study, aminosilane functionalization is employed to improve the nano-sized zeolite Y (ZeY) particle dispersion and adhesion in polyether block amide (Pebax). The performance of CO2/CH4 separation of Pebax mixed matrix composite hollow fiber membranes, incorporated with ZeY and aminosilane-modified zeolite Y (Mo-ZeY), is investigated. The addition of the zeolite filler at a small loading at 5 wt.% has a positive impact on both gas permeability and separation factor. Due to the CO2-facilitated transport effect, the performance of MMMs is further improved by the amino-functional groups modified on the ZeY. When 5 wt.% of Mo-ZeY is incorporated, the gas permeability and CO2/CH4 separation factor of the Pebax membrane are enhanced by over 100% and 35%, respectively.
Project description:Mixing a polymer matrix and nanofiller to prepare a mixed matrix membrane (MMM) is an effective method for enhancing gas separation performance. In this work, a unique UiO-66-decorated halloysite nanotubes composite material (UiO-66@HNT) was successfully synthesized via a solvothermal method and dispersed into the Pebax-1657 matrix to prepare MMMs for CO2/N2 separation. A remarkable characteristic of this MMM was that the HNT lumen provided the highway for CO2 diffusion due to the unique affinity of UiO-66 for CO2. Simultaneously, the close connection of the UiO-66 layer on the external surface of HNTs created relatively continuous pathways for gas permeation. A suite of microscopy, diffraction, and thermal techniques was used to characterize the morphology and structure of UiO-66@HNT and the membranes. As expected, the embedding UiO-66@HNT composite materials significantly improved the separation performances of the membranes. Impressively, the as-obtained membrane acquired a high CO2 permeability of 119.08 Barrer and CO2/N2 selectivity of 76.26. Additionally, the presence of UiO-66@HNT conferred good long-term stability and excellent interfacial compatibility on the MMMs. The results demonstrated that the composite filler with fast transport pathways designed in this study was an effective strategy to enhance gas separation performance of MMMs, verifying its application potential in the gas purification industry.
Project description:The key challenge in the synthesis of composite mixed matrix membrane (MMMs) is the incompatible membrane fabrication using porous support in the dry-wet phase inversion technique. The key objective of this research is to synthesize thin composite ternary (amine) mixed matrix membranes on microporous support by incorporating 10 wt% of carbon molecular sieve (CMS) and 5-15 wt% of diethanolamine (DEA) in polyethersulfone (PES) dope solution for the separation of carbon dioxide (CO2) from methane (CH4) at high-pressure applications. The developed membranes were evaluated for their morphological structure, thermal and mechanical stabilities, functional groups, as well as for CO2-CH4 separation performance at high pressure (10-30 bar). The results showed that the developed membranes have asymmetric structure, and they are mechanically strong at 30 bar. This new class of PES/CMS/DEA composite MMMs exhibited improved gas permeance compared to pure PES composite polymeric membrane. CO2-CH4 perm-selectivity enhanced from 8.15 to 16.04 at 15 wt% of DEA at 30 bar pressure. The performance of amine composite MMMs is theoretically predicted using a modified Maxwell model. The predictions were in good agreement with experimental data after applying the optimized values with AARE % = ∼less than 2% and R 2 = 0.99.
Project description:In this study, the performances of mixed matrix composite membranes (MMCMs) containing surface-treated NaX nanocrystals (ST-NaX-NCs) were experimentally and theoretically investigated for O2/N2 separation. For this purpose, the MMCMs were fabricated by the casting solution method and characterized by various analyses. The results reveal that there is a robust interaction between the polymer chains and the ST-NaX-NCs, and that the ST-NaX fillers are uniformly dispersed in the polymer matrix. The incorporation of ST-NaX-NCs alters the PEBAX polymer chain packing arrangement resulting in decreased membrane transport behavior for both O2 and N2 gases. The MMCM containing 16.7% wt ST-NaX-NCs has drastically enhanced air separation properties, with a selectivity that is increased to 204% of that of the neat membrane. Moreover, the Lewis-Nielsen model was modified by considering non-ideal effects in mixed matrix membranes, like the clogging of filler pores and polymer chain hardening around the nanocrystals, to predict the gas permeation behavior through the MMCMs. The comparison of the experimental and model results reveals that the modified model can accurately predict the gas permeability and selectivity through the MMCMs.
Project description:Although PEBAX-1657 is one of the promising polymeric materials for selective CO2 separation, there remain many questions about the optimal polymeric structure and possibility of improving performance without adulterating its basic structure by impregnating inorganic fillers. In order to improve the gas separation performance, low thickness PEBAX membranes were synthesized under steady solvent evaporation conditions by keeping in mind that one of its segments (nylon 6) shows structural variance and molecular orientation with a change in the evaporation rate. Furthermore, phase pure zeolite nanocrystals with cubic (zeolite A) and octahedral (zeolite Y) shapes have been synthesized through liquid phase routes using microwave hydrothermal reactors. The average sizes of zeolite A and Y crystals are around 55 and 40 nm, respectively. The inspection of XRD, DSC and Raman shift of PEBAX membranes demonstrates the formation of a stable polymeric structure with an improved crystalline state which results in high CO2 permeability membranes. The CO2 permeability as well as diffusivity increase with a decrease in membrane thickness and reach a maximum value of 184.7 Barrer and 2.6 × 10-6 cm2 s-1, respectively. The as-fabricated pristine PEBAX membrane shows much better performance in terms of permeance (CO2 184.7 Barrer), diffusivity (CO2 2.6 × 10-6 cm2 s-1) and selectivity (CO2/N2 59.7), which substantiate its promising prospects for CO2 capture. This exceptional performance of the pristine PEBAX membrane arises from the free volume generated during the steady polymerization. This reported approach for PEBAX membrane synthesis provides a direction in the design of membrane fabrication processes for economic CO2 separation.
Project description:Developing blend membrane material is one feasible and effective route for improving the gas separation efficiency and commercial attractiveness of membrane technologies. Here, free-standing membranes were prepared by casting method using Pebax-1074 as continuous polymer matrix and poly(ethylene glycol) (PEG) as dispersive organic fillers. The morphology, surface functional groups, microstructure and thermal stability of the membranes were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry, respectively. The effects of preparation variables including average molecular weight and dosage of PEG on the microstructure, morphology and properties of the blend membranes were investigated. In addition, the effects of operation conditions including permeation temperature and permeation pressure on the gas separation performance of the blend membranes were also examined. The results showed that the addition of PEG can obviously modify the structure-properties and significantly improve the separation performance of resultant membranes. Under the conditions of 30°C and 0.25 MPa, the optimal CO2 permeability and CO2/N2 selectivity respectively reached to 124.3Barrer and 115.8 for the blend membranes made by PEG600 with a content of 20% in Pebax-1074 matrix. In brief, the as-prepared blend membranes are proved to be promising for CO2/N2 separation application.
Project description:In this study, we investigated the effect of the addition of cellulose nanofiber (CNF) fillers on the performance of poly(lactic acid) (PLA). Modification of the hydroxyl group of cellulose to the acyl group by acid anhydrides changed the compatibility of the CNF with PLA. CNF was modified by acetic anhydride, propionic anhydride, and butyric anhydride to form surface-modified acetylated CNF (CNFa), propionylated CNF (CNFp), and butyrylated CNF (CNFb), respectively, to improve the compatibility with the PLA matrix. The effects of the different acid anhydrides were compared based on their rates of reaction in the acylation process. PLA with modified cellulose nanofiber fillers formed smoother surfaces with better transparency, mechanical, and wettability properties compared with the PLA/CNF composite film. The effects of CNFa, CNFp, and CNFb on the PLA matrix were compared, and it was found that CNFp was the best filler for PLA.
Project description:Zeolitic imidazole framework (ZIF-8) was incorporated into poly(ether-block-amide) (Pebax-1657) in differing ratios to prepare mixed matrix membranes (MMMs) for gas separation. As ZIF-8 loading is increased, gas separation selectivity also gradually increases. For economic considerations, the proportion of the increase in selectivity to the amount of MOF loaded per unit was calculated. The results show that mixing 5% MOF gives the best unit performance. With this, a variety of MOFs (UiO-66, UiO-66-NH2, A520, MIL-68(Al) and MIL-100(Fe)) were mixed with PEBAX at 5 loading to prepare MMMs. In this work, metal-organic frameworks (MOFs) were processed using the dry-free method, where in the synthesized MOF was not dried prior to incorporation. The gas separation performance test carried out shows the highest separation performance was exhibited by P-UiO-66, wherein the CO2/N2 gas selectivity was 85.94, and the permeability was 189.77 (Barrer), which was higher than Robeson's Upper bound in 2008, and obtained a high permeability and selectivity among mixed matrix membranes. In the preparation of high quality MMMs for gas separation, details regarding the interface phenomenon were assessed.
Project description:Noble metal aerogels offer a wide range of catalytic applications due to their high surface area and tunable porosity. Control over monolith shape, pore size, and nanofiber diameter is desired in order to optimize electronic conductivity and mechanical integrity for device applications. However, common aerogel synthesis techniques such as solvent mediated aggregation, linker molecules, sol⁻gel, hydrothermal, and carbothermal reduction are limited when using noble metal salts. Here, we present the synthesis of palladium aerogels using carboxymethyl cellulose nanofiber (CNF) biotemplates that provide control over aerogel shape, pore size, and conductivity. Biotemplate hydrogels were formed via covalent cross linking using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) with a diamine linker between carboxymethylated cellulose nanofibers. Biotemplate CNF hydrogels were equilibrated in precursor palladium salt solutions, reduced with sodium borohydride, and rinsed with water followed by ethanol dehydration, and supercritical drying to produce freestanding aerogels. Scanning electron microscopy indicated three-dimensional nanowire structures, and X-ray diffractometry confirmed palladium and palladium hydride phases. Gas adsorption, impedance spectroscopy, and cyclic voltammetry were correlated to determine aerogel surface area. These self-supporting CNF-palladium aerogels demonstrate a simple synthesis scheme to control porosity, electrical conductivity, and mechanical robustness for catalytic, sensing, and energy applications.
Project description:Ultrasmall 4 to 6 nm nanoparticles of the metal-organic framework (MOF) UiO-66 (University of Oslo-66) were successfully prepared and embedded into the polymer Pebax 1657 to fabricate thin-film nanocomposite (TFN) membranes for CO2/N2 and CO2/CH4 separations. Furthermore, it has been demonstrated that ligand functionalization with amino (-NH2) and nitro (-NO2) groups significantly enhances the gas separation performance of the membranes. For CO2/N2 separation, 7.5 wt % UiO-66-NH2 nanoparticles provided a 53% improvement in CO2 permeance over the pristine membrane (from 181 to 277 GPU). Regarding the CO2/N2 selectivity, the membranes prepared with 5 wt % UiO-66-NO2 nanoparticles provided an increment of 17% over the membrane without the MOF (from 43.5 to 51.0). However, the CO2 permeance of this membrane dropped to 155 GPU. The addition of 10 wt % ZIF-94 particles with an average particle size of ∼45 nm into the 5 wt % UiO-66-NO2 membrane allowed to increase the CO2 permeance to 192 GPU while maintaining the CO2/N2 selectivity at ca. 51 due to the synergistic interaction between the MOFs and the polymer matrix provided by the hydrophilic nature of ZIF-94. In the case of CO2/CH4 separation, the 7.5 wt % UiO-66-NH2 membrane exhibited the best performance with an increase of the CO2 permeance from 201 to 245 GPU.