Seeding-free synthesis of oriented zeolite LTA membrane on PDI-modified support for dehydration of alcohols

A seeding-free synthesis method is developed for preparation of oriented zeolite LTA membranes by using 1,4-phenylene diisocyanate (PDI) as a molecular linker. Before hydrothermal synthesis, –NCO groups are introduced with the functionalization of Al₂O₃ supports by PDI. A thin, well intergrown zeolite LTA membrane with a thickness of about 4.0 µm can be formed on the PDI-modified Al₂O₃ supports. The zeolite LTA membrane displays high pervaporation performances for dehydration of alcohols. At 90°C, the separation factor of the zeolite LTA membrane is 4480 for dehydration of 95 wt% ethanol/water mixtures, with a high water flux of 3.4 kg·m^?2·h^?1.     

Effect of Water Content of Synthetic Hydrogel on Dehydration Performance of Nanoporous LTA Zeolite Membranes

Nanoporous LTA‐type zeolite membranes were synthesized on α‐Al₂O₃ disk as substrate using secondary growth method. A gel formula of 1 Al₂O₃: 2 SiO₂: 3.4 Na₂O: W H₂O in molar basis was chosen while its water content (W) was varied. Four levels of water contents of 140, 155, 175, and 200 were selected for membrane synthesis. The results showed that the best membrane was synthesized with water content of 155. The most efficient zeolite membrane showed a permeation flux of 0.5 kg/m²/h and a separation factor of 3800 in dehydration of a 5/95 (wt%) water/isopropanol mixture at 298 K.     

Improvement of Zeolite T Membrane via Clear Solution Gel in Dehydration of Methanol,Ethanol, and 2-Propanol

Using of clear gel solution on synthesis of zeolite membrane can potentially have many benefits. In this research, zeolite T membrane on home-made α-Alumina disc-shaped MF support was successfully synthesized in 120°C for 24 h via secondary growth hydrothermal method using high alkalinity clear gel solution in molar ratio formulation (SiO₂:Al₂O₃:Na₂O:K₂O:H₂O = 55:1:122.7:42.3:2000). The synthesized membrane showed elevated selectivity in dehydration of ethanol/water and 2-propanol/water solutions (between 1000 to more than 10000) and high-water permeation fluxes (between 1.2 to 2.4 kg/m²h at 40°C for 10 wt.% water content). The synthesized MF alumina supports, zeolite T membranes, and crystals used for seeding were characterized by XRD and SEM analyses. These analyses indicated 10 μm dense and defect-free well-intergrowth zeolite T as active layers were formed on the porous media support.     

Synthesis at several length scales of zeolite A membranes using a continuous flow method

Zeolite A membranes were synthesized in the inner side of porous TiO₂ and α-Al₂O₃ tubular supports by a continuous method. The methodology was then used at several scales for preparing membranes on TiO₂ and α-Al₂O₃ supports with lengths of 6, 12 and 25 cm. Formation of an homogeneous zeolite film was confirmed by XRD and SEM in all supports. Single-gas permeation experiments (He, H₂, N₂ and n-C₃H₈) indicated that Knudsen diffusion was the predominant mechanism in both supports. All the synthesized membranes present high flux and moderate selectivity to water in water–ethanol mixtures.     

Methylcyclohexane dehydrogenation for hydrogen production via a bimodal catalytic membrane reactor

The dehydrogenation of methylcyclohexane (MCH) to toluene (TOL) for hydrogen production was theoretically and experimentally investigated in a bimodal catalytic membrane reactor (CMR), that combined Pt/Al₂O₃ catalysts with a hydrogen‐selective organosilica membrane prepared via sol‐gel processing using bis(triethoxysilyl) ethane (BTESE). Effects of operating conditions on the membrane reactor performance were systematically investigated, and the experimental results were in good agreement with those calculated by a simulation model with a fitted catalyst loading. With H₂ extraction from the reaction stream to the permeate stream, MCH conversion at 250°C was significantly increased beyond the equilibrium conversion of 0.44–0.86. Because of the high H₂ selectivity and permeance of BTESE‐derived membranes, a H₂ flow with purity higher than 99.8% was obtained in the permeate stream, and the H₂ recovery ratio reached 0.99 in a pressurized reactor. A system that combined the CMR with a fixed‐bed prereactor was proposed for MCH dehydrogenation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1628–1638, 2015     

Ethanol perm‐selective B‐ZSM‐5 zeolite membranes from dilute solutions

Boron‐substituted MFI (B‐ZSM‐5) zeolite membranes with high pervaporation (PV) performance were prepared onto seeded inexpensive macroporous α‐Al₂O₃ supports from dilute solution and explored for the separation of ethanol/water mixtures by PV. The effects of several parameters on microstructures and PV performance of the B‐ZSM‐5 membranes were examined systematically, including the seed size, synthesis temperature, crystallization time, B/Si ratio, H₂O/SiO₂ ratio and silica source. A continuous and compact B‐ZSM‐5 membrane was fabricated from solution containing 1 tetraethyl orthosilicate/0.2 tetrapropylammonium hydroxide/0.06 boric acid/600 H₂O at 448 K for 24 h, showing a separation factor of 55 and a flux of 2.6 kg/m² h along with high reproducibility for a 5 wt % ethanol/water mixture at 333 K. It was demonstrated that the incorporation of boron into mobile five (MFI) structure could increase the hydrophobicity of B‐ZSM‐5 membrane evidenced by the improved contact angle and amount of the adsorbed ethanol, and thus enhance the PV property for ethanol/water mixtures. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2447–2458, 2016     

The conversions of 1,3,5-trimethylbenzene over beta zeolite: Effect of SiO2/Al2O3 ratio

A series of beta zeolites with various SiO₂/Al₂O₃ ratios has been synthesized. These samples were characterized with respect to crystallinity, particle size, acidity and sorption capacities of water, n-hexane and cyclohexane. The conversion of 1,3,5-trimethylbenzene (TrMB) was conducted in a fixed bed reactor at 493–743 K and atmospheric pressure. The conversion of 1,3,5-TrMB decreased with an increase in the SiO₂/Al₂O₃ ratio of the zeolite. The zeolites with low SiO₂/Al₂O₃ ratio favored the disproportionation and the zeolites with high SiO₂/Al₂O₃ ratio favored the isomerization. These can be interpreted by the acid concentration of zeolite. In the isomerization, all zeolites produced more 1,2,4-TrMB than 1,2,3-TrMB. In the disproportionation, the selectivity of tetramethylbenzene (TeMB) was in the order of 1,2,3,5->1,2,4,5->1,2,3,4-TeMB. The concentration of 1,2,4,5-TeMB is greater than that at equilibrium. The results show that shape selectivity comes into effect. The reaction temperature and the reaction time on stream also affect the selectivity significantly due to coke formation in the zeolites. © 1998 SCI     

Pure Hydrogen and Propylene Coproduction in Catalytic Membrane Reactor-Assisted Propane Dehydrogenation

Propane dehydrogenation on a commercial Pt-Sn/Al₂O₃ catalyst in a Pd-Ag membrane reactor is considered. A mathematical model is developed to evaluate the performance of the catalytic membrane reactor for the process of propane dehydrogenation. Design and operating conditions are systematically evaluated for key performance metrics such as propane conversion, propylene selectivity, hydrogen selectivity, and hydrogen recovery under different operating conditions. The results confirm that the high performance of the membrane reactor is related to the continuous removal of hydrogen from the reaction zone to shift the reaction equilibrium towards the formation of more propylene and hydrogen.     

Upgrading of a syngas mixture for pure hydrogen production in a Pd-Ag membrane reactor

Water gas shift (WGS) is a thermodynamics limited reaction and CO equilibrium conversion of a traditional reactor is furthermore reduced owing to the presence of H₂ (ca. 50%) in the feed stream coming from a reformer.The upgrading of a simulated reformate stream was experimentally investigated as a function of temperature (280-320 °C), feed pressure (up to 600 kPa), gas hourly space velocity (GHSV), etc. using a Pd-alloy membrane reactor (MR) packed with a commercial catalyst CuO/CeO₂/Al₂O₃; no sweep gas was used. The MR performance was also evaluated using new parameters such as conversion index, H₂ recovery and extraction index, etc., which evidence the advantages with respect to a traditional reactor.A Pd-based MR operated successfully overcoming the thermodynamic constraints of a traditional reactor and, specifically, the drawback introduced by the hydrogen presence. In fact, a CO conversion of 90% significantly exceeded (three times) the thermodynamics upper limit (<36%) of a traditional reactor owing to ca. 80% of hydrogen permeated through the membrane.The overall process performance was significantly improved by the presence of the Pd-based membrane and, thus, by the high reaction pressure which allowed and drove the hydrogen permeation.     

Synthesis of NaA and NaX Zeolite Membranes by Fumed Silica Via Clear Solution Gel

NaA zeolite membranes have been used for dehydration of organic solvents in laboratory and commercial scales. There are many synthesis methods and conditions for manufacturing the membranes. The use of lactescent and clear gel solutions are two of the most important choices for high quality hydrothermal synthesis of NaA zeolite membrane in gas separation or dehydration of organic solvents. In this article, effect of hydrothermal synthesis time was investigated using the clear gel solution (Al₂O₃:5SiO₂:50Na₂O:1000H₂O). Phase transformation from NaA to NaX was recognized as the most possible event when the clear gel solution was used. XRD spectra, SEM images, and GC analyses were used for evaluation of zeolite crystal phase, the membrane layer quality, and the contents of organic substances (ethanol or 2-propanol) in feed and permeate streams in pervaporation tests, respectively. From synthesis of zeolite membrane at different times, it was revealed that for achieving the pure NaA zeolite phase the synthesis time should not exceed 3 h at 100°C.     

A comparative simulation analysis of propane dehydrogenation in composite and microporous membrane reactors

Propane dehydrogenation has been simulated for a composite membrane reactor and a microporous membrane reactor using plug‐flow reactor models, in which both were packed with Pt/Al₂O₃ catalyst in the tube‐side. The reaction kinetics employed in the analysis were obtained from experimental data produced in an integral fixed bed reactor with the same catalyst. Comparative studies were carried out to analyse the performances of reactors containing the different membranes in terms of contact time, flow pattern and flow rate of sweep gas, and pressure. In general, the composite membrane reactors gave the better performance for all cases investigated. © 2002 Society of Chemical Industry     

Synthesis and Characterization of Ceramic Membranes (W‐Type Zeolite Membranes)

In this article, effects of synthesis parameters (synthesis temperature, synthesis time, and number of layers) on W‐type zeolite membranes synthesized over flat SUS supports for O₂/SF₆ gas separation were experimentally investigated. Experiments were carried out at these levels of synthesis temperature: 165°C, 185°C, and 200°C; synthesis time: 6, 12, and 18 h and number of layers: 1 and 2. Permeation measurements, XRD and SEM analysis were used for characterization of the synthesized membranes. The results showed that increasing synthesis temperature from 165°C up to 185°C increases separation factor of O₂/SF₆, however, further increasing decreases the separation performance. The same trend was observed for synthesis time for the single layer synthesized zeolite W membrane, although for the double layer synthesized zeolite W membrane, separation factor increased with increasing synthesis time. Repetition of layering has a net positive effect on separation factor of O₂/SF₆, and negative effect on permeation flux through the membranes. This behavior was attributed to the dual effect of synthesis temperature and synthesis time on selectivity. More zeolite crystals are deposited and larger crystals are formed at higher synthesis temperatures and longer synthesis times. Well W‐type zeolite membrane was synthesized at 185°C for 18 h with two repeating layers with a high separation factor of 20.1.     

PFSA-TiO2(or Al2O3)-PVA/PVA/PAN difunctional hollow fiber composite membranes prepared by dip-coating method

PFSA-TiO₂(or Al₂O₃)-PVA/PVA/PAN difunctional hollow fiber composite membranes with separation performance and catalytic activity have been prepared by dip-coating method. The good separation performance was brought about by the glutaraldehyde (GA) surface cross-linked PVA/PAN composite membrane, and the good catalytic activity of the membrane was achieved by the perfluorosulphonic acid (PFSA) used. The difunctional hollow fiber membranes were characterized by XRD, TGA, EDX, SEM, and FTIR. The separation performance was measured by dehydration of azeotropic top product of ethanol-acetic acid esterification, and the catalytic activity was obtained by investigating the esterification of ethanol and acetic acid. The FTIR spectra and the morphologies of difunctional hollow fiber composite membranes were similar for samples prior to esterification and post-esterification with ethanol and acetic acid for 24?h. Difunctional hollow fiber composite membranes with 2% PFSA, 8% TiO₂ (named as DM-T1), and 2% PFSA, 8% Al₂O₃ (named as DM-A1) (all by weights) showed the best catalytic activity. They displayed fluxes of 165 and 173?g/m^2?h, separation factors of water to ethanol of 279 and 161, PFSA contents in difunctional hollow fiber composite membrane of 3.2 and 2.4%, the ratios of PFSA to feed solution (acetic acid?Cethanol) of 0.031 and 0.023%, and the equilibrium conversion of ethanol at 53.5 and 57.6%, in the given order for TiO₂ and Al₂O₃ containing samples.     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Upgrading of Simulated Syngas by Using a Nanoporous Silica Membrane Reactor

The permeance properties of a nanoporous silica membrane were first evaluated in a laboratory‐scale porous silica membrane reactor (MR). The results indicated that CO, CO₂, and N₂ inhibited H₂ permeation. Increased H₂ permeability and selectivity were obtained when gas was transferred from the lumen side to the shell side. This was therefore selected as a suitable permeation direction. On this basis, upgrading of simulated syngas was experimentally investigated as a function of temperature (150 – 300 °C), feed pressure (up to 0.4 MPa), and gas hourly space velocity (GHSV), by using a nanoporous silica MR in the presence of a Cu/ZnO/Al₂O₃ catalyst. The CO conversion obtained with the MR was significantly higher than that with a packed‐bed reactor (PBR) and broke the thermodynamic equilibrium of a PBR at 275 – 300 °C and a GHSV of 2665 h^–1. The use of a low GHSV and high feed pressure improved the CO conversion and led to the recovery of more H₂.     

Pure H2 production through hollow fiber hydrogen‐selective MFI zeolite membranes using steam as sweep gas

Hollow fiber MFI zeolite membranes were modified by catalytic cracking deposition of methyldiethoxysilane to enhance their H₂/CO₂ separation performance and further used in high temperature water gas shift membrane reactor. Steam was used as the sweep gas in the MR for the production of pure H₂. Extensive investigations were conducted on MR performance by variations of temperature, feed pressure, sweep steam flow rate, and steam‐to‐CO ratio. CO conversion was obviously enhanced in the MR as compared with conventional packed‐bed reactor (PBR) due to the coupled effects of H₂ removal as well as counter‐diffusion of sweep steam. Significant increment in CO conversion for MR vs. PBR was obtained at relatively low temperature and steam‐to‐CO ratio. A high H₂ permeate purity of 98.2% could be achieved in the MR swept by steam. Moreover, the MR exhibited an excellent long‐term operating stability for 100 h in despite of the membrane quality. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3459–3469, 2015     

Analysis of Membrane Reactors for Integrated Coupling of Oxidative and Thermal Dehydrogenation of Propane

This study presents strategies capable to intensify the thermal dehydrogenation of propane (TDH) using integrated reactor concepts. An inert packed bed membrane reactor for distributed dosing of oxygen to realize the oxidative dehydrogenation (ODH) was studied and compared to a reactor with catalytically active membrane. The latter concept allows to combine TDH and ODH in one apparatus to overcome the chemical equilibrium by in situ conversion of the by‐product H₂ using O₂ or in a reverse water‐gas shift reaction by CO₂. If CO₂ is used as active sweep gas the reactor offered better performance regarding yield and selectivity. Strategies for further thermal integration are discussed.     

Zeolite beta synthesized with acid-treated metakaolin and its application in diesel hydrodesulfurization

A new type of zeolite beta (denoted as MB) with multi-pore system was synthesized by using in situ synthesized method from kaolin mineral in this study. NiW/Al₂O₃–MB and NiW/TiO₂–Al₂O₃–MB catalysts were prepared and the hydrodesulfurization (HDS) activities of these catalysts were evaluated with FCC diesel feed. The samples were characterized by N₂ physisorption, XRD, SEM, TPR, FT-IR spectroscopy of pyridine adsorption, HRTEM and XPS techniques. The HDS results showed that the MB-containing catalyst exhibited much higher HDS conversion (98.7%) than that of NiW/γ-Al₂O₃ (97.5%). The incorporation of TiO₂ into the composite supports further increased the HDS conversion (99.3%) of NiW/TiO₂–Al₂O₃–MB. The higher HDS activity was mainly associated with the appropriate ratio of B/L (Brönsted acid/Lewis acid) and the enhanced hydrogenation activity.     

Kinetics and Reactor Modeling of the Steam Reforming of Methanol over a Mn‐Promoted Cu/Al Catalyst

The kinetics of the steam reforming of methanol (SRM) was studied in a packed‐bed reactor over a Mn‐promoted Cu/Al₂O₃ catalyst under defined conditions. A Langmuir‐Hinshelwood‐Hogan‐Watson (LHHW)‐type mechanism that assumes the dissociative adsorption of methanol on two distinct active sites as the rate‐controlling step was found to satisfactorily describe the SRM reaction with activation energies of 77.3 and 64.5 kJ mol^?1 at low and high temperature, respectively. No mass or heat transfer limitations were observed under the experimental conditions used in this study. A reactor model was also developed, validated, and employed to predict the conversion, temperature, and concentration profiles. The axial dispersion had no influence on the temperature distribution but the effect was more pronounced on the methanol conversion.     

Hexane activation over vanadium modified zeolite ZSM-5

The influence on the form of ZSM-5, vanadium content and the elimination of the exterior surface, on the activity and selectivity of n-hexane oxidation was studied using a fixed bed reactor. Blank reactor studies (carborundum packed reactor) showed no conversion below 450 °C with the highest conversion (8 %) at 500 °C. The dominant products were found to be carbon oxides (Sel./% = 90) with minor selectivities to the hexene isomers (7 %) with the remainder being cracked products, THF and benzene. H-ZSM-5 with different SiO₂/Al₂O₃ ratios (100 and 320) and Na-ZSM-5 (SiO₂/Al₂O₃ ratio of 100) were tested under non-oxidative conditions. As the ratio of the SiO₂/Al₂O₃ increased the aluminium content decreases and so too does the cracking ability of the zeolite (i.e. yield of cracked products dropped from 36 to 8 %). However, the use of the Na- form of the ZSM-5 zeolite completely eliminated acid cracking and therefore this system was further investigated. Na-V-ZSM-5 (~1 % loading) was synthesized using the solid state ion-exchange method. Time on stream experiments (fresh batch of catalyst for each experiment with sampling at the same time for a period of 24 h) were conducted and temperature (350, 400 and 450 °C), contact time (0.5, 0.8, 1.1 and 1.5 s) and fuel/air ratios (0.7, 1.3 and 2) were varied. The optimum conditions (Conv./% = 39) for terminal functionalised products were found to be at 400 °C at a contact time of 1.1 s and a fuel air ratio of 1.3. With the lower fuel air ratio of 0.7 (oxygen rich conditions), hexanal formation was favoured.