Search Results (16)

This study focuses on optimizing the Reverse Water Gas Shift (RWGS) reaction system using a membrane reactor to improve CO₂ conversion efficiency. A one-dimensional simulation model was developed using FlexPDE Professional Version 8.01/W64 software to analyze the performance of ZSM-5 membranes integrated with 0.5 wt% Ru-Cu/ZnO/Al₂O₃ catalysts. The results show that the membrane reactor significantly outperforms the conventional Packed Bed Reactor by achieving higher CO₂ conversion (0.61 vs. 0.99 with optimized parameters), especially at lower temperatures, due to its ability to remove H₂O and shift the reaction equilibrium selectively. Key operational parameters, including temperature, pressure, and sweep gas flow rate, were optimized to maximize membrane reactor performance. The ZSM-5 membrane showed strong H₂O selectivity, with an optimum operating temperature of around 400–600 °C. The problem is that many reactants permeate at higher temperatures. Subsequently, a Half-MPBR design was introduced. This design was able to overcome the reactant permeation problem and increase the conversion. The conversion ratios for PBR, MPBR, and Half-MPBR are 0.71, 0.75, and 0.86, respectively. This work highlights the potential of membrane reactors to overcome the thermodynamic limitations of RWGS reactions and provides valuable insights to advance Carbon Capture and Utilization technologies. Full article

NaZSM-5 powder and membranes were hydrothermally prepared. Their (1) steam (H₂O) adsorption properties and (2) the permeation and separation of gas and H₂O were evaluated before and after the cation exchange of Na⁺ to K⁺ or Cs⁺. The quantity of adsorbed H₂O decreased as the size of the cation increased, indicating that the micropore volume and effective pore size of ZSM-5 decreased after cation exchange. The H₂ and N₂ permeances after cation exchange were less than 5% of the values before cation exchange, indicating a significant reduction in gas permeability. In contrast, the reduction of the H₂O permeance values of the ZSM-5 membranes before and after K⁺ or Cs⁺ exchange was lower than that of H₂, resulting in improved H₂O/H₂ separation performance. Compared with the NaZSM-5 membrane, the K⁺- or Cs⁺-exchanged ZSM-5 membranes exhibited superior H₂O permselectivity, particularly at dilute H₂O concentrations (<1 vol%). Full article

Membrane-based pervaporation (PV) for organic solvent dehydration is of great significance in the chemical and petrochemical industries. In this work, high-aluminum ZSM-5 zeolite membranes were synthesized by a fluoride-assisted secondary growth on α-alumina tubular supports using mordenite framework inverted (MFI) nanoseeds (~110 nm) and a template-free synthesis solution with a low Si/Al ratio of 10. Characterization by XRD, EDX, and SEM revealed that the prepared membrane was a pure-phase ZSM-5 zeolite membrane with a Si/Al ratio of 3.8 and a thickness of 2.8 µm. Subsequently, two categories of PV performance parameters (i.e., flux versus separation factor and permeance versus selectivity) were used to systematically examine the effects of operating conditions on the PV dehydration performance of different organic solvents (methanol, ethanol, n-propanol, and isopropanol), and their PV mechanisms were explored. Employing permeance and selectivity effectively disentangles the influence of operating conditions on PV performance, thereby elucidating the inherent contribution of membranes to separation performance. The results show that the mass transfer during PV dehydration of organic solvents was mainly dominated by the adsorption–diffusion mechanism. Furthermore, the diffusion of highly polar water and methanol molecules within membrane pores had a strong mutual slowing-down effect, resulting in significantly lower permeance than other binary systems. However, the mass transfer process for water/low-polar organic solvent (ethanol, n-propanol, and isopropanol) mixtures was mainly controlled by competitive adsorption caused by affinity differences. In addition, the high-aluminum ZSM-5 zeolite membrane exhibited superior PV dehydration performance for water/isopropanol mixtures. Full article

Solid polymer electrolytes (SPEs) are the key components of lithium metal batteries to overcome the obstacle of insecurity in conventional liquid electrolytes; however, the trade-off between their ionic conductivity and mechanical properties remains a significant challenge. In this work, two-dimensional ZSM-5 nanosheets as fillers are incorporated into a poly(ethylene oxide) (PEO) matrix and lithium salts to obtain composite polymer electrolytes (CPEs). The improved physicochemical and electrochemical properties of the CPE membranes are characterized in full detail. Stripping/plating measurements in symmetric Li/Li cells and cyclic charge/discharge tests are performed to investigate the cyclability and stability of the CPEs. All-solid-state LiFePO₄/Li batteries deliver excellent cycling performance with an initial discharge capacity of 152.3 mAh g⁻¹ and 91.4% capacity retention after 200 cycles at 0.2 C, with a discharge specific capacity of 118.8 mAh g⁻¹ remaining after 350 cycles at 0.5 C. Therefore, CPEs containing ZSM-5 nanosheets are a promising option for all-solid-state lithium-ion batteries. Full article

The hydrophobic nature of inorganic zeolite particles plays a crucial role in the efficacy of mixed matrix membranes (MMMs) for the separation of trichloroethylene (TCE) through pervaporation. This study presents a novel approach to further augment the hydrophobicity of ZSM-5. The ZSM-5 zeolite molecular sieve was subjected to modification using three different silane coupling agents, namely, n-octyltriethoxysilane (OTES), γ-methacryloxypropyltrimethoxysilane (KH-570), and γ-aminopropyltriethoxysilane (KH-550). The water contact angles of the resulting OTES@ZSM-5, KH-570@ZSM-5, and KH-550@ZSM-5 particles exhibited significant increases from 97.2° to 112.8°, 109.1°, and 102.7°, respectively, thereby indicating a notable enhancement in hydrophobicity. Subsequently, mixed matrix membranes (MMMs) were fabricated by incorporating the aforementioned silane-modified ZSM-5 particles into polydimethylsiloxane (PDMS), leading to a considerable improvement in the adsorption selectivity of these membranes towards trichloroethylene (TCE). The findings indicate that the PDMS membrane with a 20 wt.% OTES@ZSM-5 particle loading exhibits superior pervaporation performance. When subjected to a temperature of 30 °C, flow rate of 100 mL/min, and vacuum of 30 Kpa, the separation factor and total flux of a 3 × 10⁻⁷ wt.% TCE solution reach 328 and 155 gm⁻²·h⁻¹, respectively. In comparison to the unmodified ZSM-5/PDMS membrane, the separation factor demonstrates a 41% increase, while the TCE flux experiences a 6% increase. Consequently, this approach effectively enhances the pervaporation separation capabilities of the PDMS membrane for TCE. Full article

The conceptual design and engineering of an integrated catalytic reactor requires a thorough understanding of the prevailing mechanisms and phenomena to ensure a safe operation while achieving desirable efficiency and product yields. The necessity and importance of these requirements are demonstrated in this investigation in the case of novel membrane-assisted reactors tailored for CO₂ hydrogenation. Firstly, a carbon molecular sieve membrane was developed for simultaneous separation of CO₂ from a hot post-combustion CO₂-rich stream, followed by directing it along a packed-bed of hybrid CuO-ZnO/ZSM5 catalysts to react with hydrogen and produce DiMethyl Ether (DME). The generated water is removed from the catalytic bed by permeation through the membrane which enables reaction equilibrium shift towards more CO₂-conversion. Extra process intensification was achieved using a membrane-assisted reactive distillation reactor, where similarly several such parallel membranes were erected inside a catalytic bed to form a reactive-distillation column. This provides the opportunity for a synchronized separation of CO₂ and water by a membrane, mixing the educts (i.e., hydrogen and CO₂) and controlling the reaction along the catalytic bed while distilling the products (i.e., methanol, water and DME) through the catalyst loaded column. The hybrid catalyst and carbon molecular sieve membrane were developed using the synthesis methods and proved experimentally to be among the most efficient compared to the state-of-the-art. In this context, selective permeation of the membrane and selective catalytic conversion of hybrid catalysts under the targeted operating temperature range of 200–260 °C and 10–20 bar pressure were studied. For the membrane, the obtained high flux of selective CO₂-permeation was beyond the Robeson upper bound. Moreover, in the hybrid catalytic structure, a combined methanol and DME yield of 15% was secured. Detailed results of catalyst and membrane synthesis and characterization along with catalyst test and membrane permeation tests are reported in this paper. The performance of various configurations of integrated catalytic and separation systems was studied through an experimentally supported simulation along with the systematic analysis of the conceptual design and operation of such reactive distillation. Focusing on the subnano-/micro-meter scale, the performance of sequential reactions while considering the interaction of the involved catalytic materials on the overall performance of the hybrid catalyst structure was studied. On the same scale, the mechanism of separation through membrane pores was analyzed. Moreover, looking at the micro-/milli-meter scale in the vicinity of the catalyst and membrane, the impacts of equilibrium shift and the in-situ separation of CO₂ and steam were analyzed, respectively. Finally, at the macro-scale separation of components, the impacts of established temperature, pressure and concentration profiles along the reactive distillation column were analyzed. The desired characteristics of the integrated membrane reactor at different scales could be identified in this manner. Full article

Single crystalline ZSM-5 ZNs with thicknesses around 6 nm were obtained by secondary growth of silicalite nanoparticles using diquaternary bis-1,5(tripropyl ammonium) pentamethylene diiodide (dC₅) as a structure-directing agent (SDA). The dC₅ could be effectively removed from the ZN pores by either high-temperature calcination or UV irradiation in air at room temperature but not by the piranha solution treatment. Ultrathin ZN-laminated membranes (ZNLMs) were fabricated by sandwiching a UV-activated multilayered ZN film between two recast Nafion^® layers (ZNLM-Nafion) and by filtration coating from a suspension of thermally activated ZNs on a nonionic porous PVDF (ZNLM-PVDF). The ZNLMs on both supports demonstrated the ability of highly proton-selective ion conduction with low resistances in aqueous electrolyte solutions. The ZNLM-PVDF with PVDF binder was structurally stable, and it achieved a comparably low ASR but much higher proton selectivity compared with a Nafion membrane of same overall thickness. However, detachment between the ZNLM and Nafion layers occurred when the ZNLM-Nafion operated in aqueous electrolyte solutions. Results of this study show the potential for developing ZNLMs as efficient proton-conducting membranes without using expensive ionic polymer matrices. However, the development of polymer-supported ZNLMs is hindered by the current inefficiency in preparing well-dispersed suspensions of open-pore ZNs. Future development of efficient methods for synthesizing open-pore ZNs in dispersed states is key to realizing high-performance ZNLMs on polymers. Full article

Reverse water gas shift (RWGS) is attracting attention as one of the promising technologies for CO₂ conversion. Selective removal of H₂O from the reaction system can improve the CO₂ conversion beyond the equilibrium conversion of RWGS in a conventional reactor. In this study, a conventional plug-flow reactor without membrane, and two types of RWGS membrane reactors using ZSM-5 membranes, were developed. The yield of CO without membrane (Case 1) was almost the same as the equilibrium conversion. A membrane reactor (Case 2) showed a CO yield 2–3% above that of a conventional reactor. From the results, the effectiveness of the dehydration membrane reactor for RWGS was verified. In addition, CO yield was further increased in the reactor made up of the combination of conventional reactor and membrane reactor (Case 3). For example, the CO yields in Cases 1, 2, and 3 at 560 K were 21.8, 24.9, and 29.0%, respectively. Although the CO yield increased in Case 2, a large amount of raw materials penetrated through the membrane to the permeation side, and was lost. In Case 3, H₂ and CO₂ permeation through the membrane were suppressed because of the existence of H₂O, resulting in the prevention of the leakage of raw material, and contributing to the high CO yield. Full article

Fabrication of the ZSM-22/Polyethersulfone (ZSM-22/PES) membranes as selective salt filters represent a growing membrane technological area in separation with the potential of high economic reward based on its low energy requirements. The incorporation of ZSM-22 zeolite material as additives into the PES polymer matrix has the prospective advantage of combining both the zeolite and polymer features while overcoming the limitations associated with both materials. This work investigated the influence of the nature of the silica precursor on ZSM-22 zeolite hydrothermally synthesised using colloidal (C60) and fumed (C60) silica to Si/Al of 60. The successful synthesis of the highly crystalline zeolitic materials was confirmed through XRD, FTIR, and SEM with EDX. The ZSM-22 additives were directly dispersed into a PES polymeric matrix to form a casting solution for the preparation of the ZSM-22/PES selective substrate layers via a phase inversion method for salts rejection. The polymeric PES was selected as an organic network in which the content of the ZSM-22 zeolite (ranging between 0 and 1.0 wt.%), was obtained and characterised by XRD, FTIR, and SEM analysis, as well as water contact angle (WCA) measurement and dead-end filtration cell. The phase inversion preparation method has induced the resulting ZSM-22/PES NF substrates anisotropy, as attributed to a high water flux to the above 700 L·m⁻²·h⁻¹; high selectivity and rejection of salts to above 80% is revealed by the obtained results. The materials also exhibited improved antifouling behavior to above 70% flux recovery ratios. As such, the nature of the silica precursor influences ZSM-22 zeolite synthesis as a potential additive in the PES polymer matrix and led to the enhanced performance of the pure PES ultrafiltration membrane. Full article

We developed Mixed Matrix Membrane Adsorbers (MMMAs) formed by cellulose acetate and various sorbent particles (activated carbon, zeolites ZSM-5 and clinoptilolite) for the removal of urea, creatinine and uric acid from aqueous solutions, to be used in the regeneration of spent dialysate water from Hemodialysis (HD). This process would allow reducing the disproportionate amount of water consumed and permits the development of closed-loop HD devices, such as wearable artificial kidneys. The strategy of MMMAs is to combine the high permeability of porous membranes with the toxin-capturing ability of embedded particles. The water permeability of the MMMAs ranges between 600 and 1500 L/(h m² bar). The adsorption of urea, the limiting toxin, can be improved of about nine times with respect to the pure cellulose acetate membrane. Flow experiments demonstrate the feasibility of the process in a real HD therapy session. Full article

The synthesis of DDR-type zeolite membranes faces the problem of cracks that occur on the zeolite membrane due to differences in the thermal expansion coefficient between zeolite and the porous substrate during the detemplating process. In this study, Al-containing ZSM-58 zeolite membranes with DDR topology were prepared by rapid thermal processing (RTP), with the aim of developing a reproducible method for preparing DDR zeolite membrane without cracks. Moreover, we verified the influence of RTP before performing conventional thermal calcination (CTC) on ZSM-58 membranes with various silica-to-aluminum (Si/Al) molar ratios. Using the developed method, an Al-containing ZSM-58 membrane without cracks was obtained, along with complete template removal by RTP, and it had higher CO₂/CH₄ selectivity. An all-silica ZSM-58 membrane without cracks was obtained by only using the ozone detemplating method. ZSM-58 crystals and membranes with various Si/Al molar ratios were analyzed by using Fourier-transform infrared (FTIR) spectroscopy to confirm the effects of RTP treatment. Al-containing ZSM-58 zeolites had higher silanol concentrations than all-silica zeolites, confirming many silanol condensations by RTP. The condensation of silanol forms results in the formation of siloxane bonds and stronger resistance to thermal stress; therefore, RTP caused crack suppression in Al-containing ZSM-58 membranes. The results demonstrate that Al-containing ZSM-58 zeolite membranes with high CO₂ permeance and CO₂/CH₄ selectivity and minimal cracking can be produced by using RTP. Full article

The separation of CO₂ from gas streams is a central process to close the carbon cycle. Established amine scrubbing methods often require hot water vapour to desorb the previously stored CO₂. In this work, the applicability of MFI membranes for H₂O/CO₂ separation is principally demonstrated by means of realistic adsorption isotherms computed by configurational-biased Monte Carlo (CBMC) simulations, then parameters such as temperatures, pressures and compositions were identified at which inorganic membranes with high selectivity can separate hot water vapour and thus make it available for recycling. Capillary condensation/adsorption by water in the microporous membranes used drastically reduces the transport and thus the CO₂ permeance. Thus, separation factors of α_H2O/CO2 = 6970 could be achieved at 70 °C and 1.8 bar feed pressure. Furthermore, the membranes were tested for stability against typical amines used in gas scrubbing processes. The preferred MFI membrane showed particularly high stability under application conditions. Full article

Broad industrial application of zeolites increases the opportunity of inhalation. However, the potential impact of different types and compositions of zeolite on cytotoxicity is still unknown. Four types of synthetic zeolites have been prepared for assessing the effect on lung fibroblast: two zeolite L (LTL-R and LTL-D), ZSM-5 (MFI-S), and faujasite (FAU-S). The cytotoxicity of zeolites on human lung fibroblast (IMR-90) was assessed using WST1 cell proliferation assay, mitochondrial function, membrane leakage of lactate dehydrogenase, reduced glutathione levels, and mitochondrial membrane potential were assessed under control. Intracellular changes were examined using transmission electron microscopy (TEM). Toxicity-related gene expressions were evaluated by PCR array. The result showed significantly higher toxicity in IMR-90 cells with FAU-S than LTL-R, LTL-D and MFI-S exposure. TEM showed FAU-S, spheroidal zeolite with a low Si/Al ratio, was readily internalized forming numerous phagosomes in IMR-90 cells, while the largest and disc-shaped zeolites showed the lowest toxicity and were located in submembranous phagosomes in IMR-90 cells. Differential expression of TNF related genes was detected using PCR arrays and confirmed using qRT-PCR analysis of selected genes. Collectively, the exposure of different zeolites shows different toxicity on IMR-90 cells. Full article

Commercial separators (polyolefin separators) for lithium-ion batteries still have defects such as low thermostability and inferior interface compatibility, which result in serious potential safety distress and poor electrochemical performance. Zeolite/Polyacrylonitrile (Z/PAN) composite separators have been fabricated by electrospinning a polyacrylonitrile (PAN) membrane and then dip-coating it with zeolite (ZSM-5). Different from commercial separators, the Z/PAN composite separators exhibit high electrolyte uptake, excellent ionic conductivity, and prominent thermal stability. Specifically, the Z/PAN-1.5 separator exhibits the best performance, with a high electrolyte uptake of 308.1% and an excellent ionic conductivity of 2.158 mS·cm⁻¹. The Z/PAN-1.5 separator may mechanically shrink less than 10% when held at 180 °C for 30 min, proving good thermal stability. Compared with the pristine PAN separator, the Li/separator/LiFePO₄ cells with the Z/PAN-1.5 composite separator have excellent high-rate discharge capacity (102.2 mAh·g⁻¹ at 7 C) and favorable cycling performance (144.9 mAh·g⁻¹ at 0.5 C after 100 cycles). Obviously, the Z/PAN-1.5 separator holds great promise in furthering the safety and performance of lithium-ion batteries. Full article

ZSM-22/polyethersulfone membranes were prepared for salt rejection using modelled brackish water. The membranes were fabricated via direct ZSM-22 incorporation into a polymer matrix, thereby inducing the water permeability, hydrophilicity and fouling resistance of the pristine polyethersulfone (PES) membrane. A ZSM-22 zeolite material with a 60 Si/Al ratio, high crystallinity and needle-like morphologies was produced and effectively used as a nanoadditive in the development of ZSM-22/PES membranes with nominal loadings of 0–0.75 wt.%. The characterisation and membrane performance evaluation of the resulting materials with XRD, BET, FTIR, TEM, SEM and contact angle as well as dead-end cell, respectively, showed improved water permeability in comparison with the pristine PES membrane. These ZSM-22/PES membranes were found to be more effective and superior in the processing of modelled brackish water. The salt rejection of the prepared membranes for NaCl and MgCl₂ was effective, while they exhibited quite improved water flux and flux recovery ratios in the membrane permeability and anti-fouling test. This indicates that different amounts of ZSM-22 nanoadditives produce widely divergent influences on the performance of the pristine PES membrane. As such, over 55% of salt rejection is observed, which means that the obtained membranes are effective in salt removal from water. Full article