SAPO-34 membranes for CO2/CH4 separations: Effect of Si/Al ratio

Silicoaluminophosphate (SAPO) membranes with Si/Al gel ratios from 0.05 to 0.3 were synthesized by in situ crystallization onto porous, tubular stainless steel support. Pure SAPO-34 membranes were obtained when the Si/Al ratio was 0.15 or higher. The adsorbate polarizability correlated with the adsorption capacity on SAPO-34, and the amounts of gases adsorbed were in the order: CO₂ > CH₄ > N₂ > H₂. The Si/Al ratio did not affect the pore volume significantly, but it changed the CO₂ and CH₄ adsorption equilibrium constants. The SAPO-34 membranes effectively separated CO₂ from CH₄ for feed pressures up to 7 MPa. At 295 K, for a pressure drop of 138 kPa and a 50/50 feed, the CO₂/CH₄ selectivity was 170 for a membrane with a Si/Al gel ratio of 0.15. At 7 MPa, the CO₂/CH₄ selectivity was 100 and the CO₂ permeance was 4 × 10⁻⁸ mol/(m² · s · Pa) at 295 K. This membrane was also separated CO₂/N₂ (selectivity = 21) and H₂/CH₄ (selectivity = 32) mixtures at 295 K and a pressure drop of 138 kPa. Competitive adsorption and difference in diffusivities are responsible for CO₂/CH₄ and CO₂/N₂ separations, whereas the H₂/CH₄ separation was due to diffusivity differences. For a membrane with Si/Al gel ratio of 0.1, a mixture of SAPO-34 and SAPO-5 formed, and the CO₂/CH₄ selectivity was lower.     

Reversible H2 storage using a SAPO-34 zeolite layer

A SAPO-34 zeolite membrane was made essentially impermeable to high-pressure hydrogen at room temperature by adsorbing methanol in the SAPO-34 layer. Hydrogen permeance decreased three orders of magnitude when the methanol feed activity was 0.1, and it decreased more than six orders of magnitude when the methanol feed activity was higher than 0.85 at 293 K. The hydrogen permeance at 293 K was below 10⁻¹⁴ mol/m² s Pa for at least five days for a H₂ feed pressure of 6.6 MPa. At higher temperatures, methanol desorbed and the H₂ flux increased. The hydrogen permeance could be controlled by the activity of the methanol on the feed side. These results demonstrate that the SAPO-34 membrane had low fluxes through defects, and H₂ flow through these defects was blocked by capillary condensation of methanol at high methanol activities.     

On-stream modification of MFI zeolite membranes for enhancing hydrogen separation at high temperature

-Alumina-supported MFI zeolite membranes were modified by on-stream catalytic thermal cracking of methyldiethoxysilane (MDES) molecules inside the zeolitic channels during the separation of H₂/CO₂ gas mixture at 450 °C and atmospheric pressure. The MDES vapor was carried by the H₂/CO₂ feed gas and the effect of modification was monitored continuously through online analysis of the permeate stream. The modified membrane exhibited a significant increase in H₂ selectivity over CO₂ with a moderate decrease in H₂ permeance. At 450 °C, the modified MFI membrane obtained a H₂/CO₂ permselectivity of 17.5 with H₂ single gas permeance of 1.86 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ as compared to a permselectivity of 2.78 and permeance of 2.75 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ for the membrane before modification. The modified membrane also showed good performance and stability in separation of H₂/CO₂ gas mixture containing up to 28.4% water vapor at 450 °C and atmospheric pressure.     

Synthesis and permeation properties of ion-exchanged ETS-4 tubular membranes

Zeolite membranes, which were composed of ETS-4 with Na cations, were prepared on porous -alumina tubes by hydrothermal synthesis. The membranes, which were formed under optimized conditions, sharply rejected molecules with sizes larger than 0.4 nm. For mixtures of N₂–CO₂, N₂–O₂, N₂–Ar and N₂–CH₄ systems, N₂ permeated faster than the coexisting gas. The N₂/O₂ separation factor for an equimolar mixture was in the range of 2.3–3.5, and the N₂ permeance was in the range of (0.55–2.8)×10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ at permeation temperatures of 283–333 K. Moisture had some effect on the permeation properties for N₂–O₂ mixtures. The separation factor for the N₂/CH₄ system was larger than that of the N₂/O₂ system. When the membrane was ion exchanged with either Li⁺ or Sr²⁺, the separation factors for N₂/O₂ and N₂/CH₄ systems increased, while the permeances decreased.     

Selective permeation and separation of steam from water–methanol–hydrogen gas mixtures through mordenite membrane

Separation properties of a mordenite membrane for water–methanol–hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49–156 and 73–101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹ up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 503 K and reached to 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol.     

Modeling CO2-facilitated transport across a diethanolamine liquid membrane

We compared experimental and model data for the facilitated transport of CO₂ from a CO₂–air mixture across an aqueous solution of diethanolamine (DEA) via a hollow fiber, contained liquid membrane (HFCLM) permeator. A two-step carbamate formation model was devised to analyze the data instead of the one-step mechanism used by previous investigators. The effects of DEA concentration, liquid membrane thickness and feed CO₂ concentration were also studied. With a 20% (wt) DEA liquid membrane and feed of 15% CO₂ in CO₂–air mixture at atmosphere pressure, the permeance reached 1.51E−8 mol/m² s Pa with a CO₂/N₂ selectivity of 115. Model predictions compared well with the experimental results at CO₂ concentrations of industrial importance. Short-term stability of the HFCLM permeator performance was examined. The system was stable during 5-days of testing.     

Sorption kinetics of ammonia and ammonium ions on gel and macroporous sulphonic acid cation exchangers

Diffusion of ammonia and ammonium ions in sulphonic acid cation exchangers (gel Purolite SGC 100 × 10 MBH and macroporous Purolite C 160 MBH) from the solutions, representing the composition of “caustic condensate” (waste of nitrogen fertilizers production) is affected by pH of initial solution and structure of the matrix of cation exchanger. In gel matrix the effective intraparticle diffusivity (D_ef) depends greatly on the solution pH because of shrinkage in alkaline and swelling in acidic medium: on decreasing the initial concentration of ammonia from 0.214 to 0.003 and increasing that of ammonium nitrate from 0 to 0.214 mol l⁻¹ instead, the effect of ion exchange leads to a decrease in pH, resulting in swelling and increase in D_ef from 0.1 to 0.34 × 10⁻¹⁰ for gel Purolite SGC 100 × 10 MBH and variation of 0.18–0.11 × 10⁻¹⁰ m² s⁻¹ for macroporous Purolite C 160 MBH (resistant to shrinkage and swelling).

In Purolite C 160 MBH both macropore diffusivity (0.07–0.29 × 10⁻¹⁰ m² s⁻¹) and gel (solid phase) diffusivity (0.06–0.19 × 10⁻¹⁰ m² s⁻¹) are higher than micropore diffusivity (0.28–0.56 × 10⁻¹⁸ m² s⁻¹).

With respect to the effective intraparticle diffusivity, resistance to nitric acid, used for the regeneration, and high concentration of ammonium nitrate in eluate (up to 110 g l⁻¹), Purolite C 160 MBH has been installed for the conversion of ammonia and ammonium ions to ammonium nitrate reusable in the fertilizers production. This allows minimizing the economic loss and preventing the environmental contamination.     

Influence of exchanged cations (Na, Cs, Sr and Ba) on xylene permeation through ZSM-5/SS tubular membranes

Na-ZSM-5 membranes were synthesized by secondary growth on the outer surface of stainless steel porous tubes. The membranes were ion-exchanged with Cs⁺, Ba²⁺ and Sr²⁺ to investigate their effect upon the separation of p-xylene from m-xylene and o-xylene. The permeation through the membranes was measured between 150 and 400 °C using each xylene isomer separately and a ternary mixture. All the membranes were selective to p-xylene in the temperature range studied. N₂ and xylene permeation measurements together with SEM observations were used to determine whether or not cracks and/or pinholes developed after exposure to the xylene isomers at high temperature (400 °C). Neither pore blockage nor extra-zeolitic pores developed after the ion exchange procedure and subsequent calcination. Furthermore, duplicate synthesized membranes of each cation form had similar separation factors and permeances. The duplicate values differ much less than the measurement error. The p-xylene permeation flux decreased in the order: Na-ZSM-5 > Ba-ZSM-5 > Sr-ZSM-5  Cs-ZSM-5 while the permeation flux of the m- and o-xylene decreased in the order Na-ZSM-5 > Sr-ZSM-5 > Ba-ZSM-5 > Cs-ZSM-5. The membrane that exhibited the best performance was Ba-ZSM-5, with a maximum p/o separation factor of 8.4 and a p-xylene permeance of 0.54 × 10⁻⁷ mol s⁻¹ m⁻² Pa⁻¹ at 400 °C.     

Reduction of nitrite by sulfamic acid and sodium azide from aqueous solutions treated by gliding arc discharge

Nitrous and nitric acids form in aqueous solutions exposed to a gliding arc discharge burning in humid air. The anions interfere when the concentration of particular solutes such as pollutants must be determined. In particular they falsify the COD measurements and spectral investigations and thus the efficiency of the plasma treatment in pollutant abatement. The nitrite anions must be thus removed, which require specific reagents. The influence of parameters such as solution pH and [reducers]/[NO₂⁻] ratio on the reduction reaction was evaluated. The reduction of nitrite into N₂ either by sulfamic acid or sodium azide is a first-order pH-dependant reaction with regard to nitrite and reducers (k₁ = 2.93 × 10⁻¹ m³ kmol⁻¹ s⁻¹; k₂ = 6.21 × 10⁻¹ m³ kmol⁻¹ s⁻¹, respectively). Sodium azide is thus more reactive than sulfamic acid.     

High-quality, oriented and mesostructured organosilica monolith as a potential UV sensor

We synthesized high-quality and oriented periodic mesoporous organosilica (PMO) monoliths through a solvent evaporation process using a wide range of mole ratios of the components: 0.17–0.56 1,2-bis(triethoxysilyl)ethane (BTSE): 0.2 cetyltrimethylammonium chloride (CTACl): 0–1.8 × 10⁻³ HCl: 0–80 EtOH: 5–400 H₂O. X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) images indicated that the mesoporous channels within the monolith samples were oriented parallel to the flat external surface of the PMO monolith and possessed a hexagonal symmetry lattice (p6mm). The PMO monolith synthesized from a reactant composition of 0.35 BTSE: 0.2 CTACl: 1.8 × 10⁻⁶ HCl: 10 EtOH: 10 H₂O had a pore diameter, pore volume, and surface area – obtained from an N₂ sorption isotherm – of 25.0 Å, 0.96 cm³ g⁻¹ and 1231 m² g⁻¹, respectively. After calcination at 280 °C for 2 h in N₂ flow, the PMO monolith retained monolith-shape and mesostructure. Pore diameter and surface area of the calcined PMO monolith sample were 19.8 Å, 0.53 cm³ g⁻¹ and 1368 m² g⁻¹, respectively. We performed ²⁹Si and ¹³C CP MAS NMR spectroscopy experiments to confirm the presence of Si–C bonding within the framework of the PMO monoliths. We investigated the thermal stability of the PMO monoliths through thermogravimetric analysis (TGA). In addition, rare-earth ions (Eu³⁺, Tb³⁺ and Tm³⁺) were doped into the monoliths. Optical properties of those Eu³⁺, Tb³⁺ and Tm³⁺-doped PMO monoliths were investigated by photoluminescence (PL) spectra to evaluate their potential applicability as UV sensors.     

High-performance SSZ-13 membranes prepared using ball-milled nanosized seeds for carbon dioxide and nitrogen separations from methane

SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis. Separation performances of SSZ-13 membranes in CO_2/CH_4 and N_2/CH_4 mixtures were enhanced after synthesis modification. Single-gas permeances of CO_2, N_2 and CH_4 and ideal selectivities were recorded through SSZ-13 membranes. The effects of temperature, pressure, feed flow rate and humidity on separation performance of the membranes were discussed. Three membranes prepared after synthesis modifications had an average CO_2 permeance of 1.16 × 10~(-6) mol·(m~2· s·Pa)~(-1)(equal to 3554 GPU) with an average CO_2/CH_4 selectivity of 213 in a 50 vol%/50 vol% CO_2/CH_4 mixture. It suggests that membrane synthesis has a good reproducible. The membrane also displayed a N_2 permeance of 1.07 × 10~(-7) mol·(m~2·s·Pa)~(-1)(equal to 320 GPU) with a N_2/CH_4 selectivity of 13 for a 50 vol%/50 vol% N_2/CH_4 mixture. SSZ-13 membrane displayed stable and good separation performance in the wet CO_2/CH_4 mixture for a long test period over 100 h at 348 K. The current SSZ-13 membranes show great potentials for the simultaneous removals of CO_2 and N_2 in natural gas purification as a facile process suitable for industrial application.     

Effects of oxygen concentration on the electrical properties of ZnO films

In this paper, electrical characteristics by various oxygen content in ZnO films were studied. To control the oxygen content of ZnO films, post-thermal annealing was performed in N₂ and air ambient, led to improve crystallinity and optical properties of ZnO films. The oxygen concentration was measured by Auger electron spectroscopy. The ZnO films having the deficiency of oxygen showed the electron concentrations between 10²¹ and mid 6 × 10¹⁷ cm⁻³ and resistivity at 10⁻³–10⁻¹ Ω cm. On the other hand, when the oxygen concentration of the ZnO films was up to the stoichiometry with Zn, the ZnO films showed low electron concentration at −10¹⁷ cm⁻³ and resistivity at 10 Ω cm.     

Separation and enrichment of carbon dioxide by capillary membrane module with permeation of carrier solution

A novel facilitated transport membrane for gas separation using a capillary membrane module is proposed in which a carrier solution is forced to permeate the membrane. Both a feed gas and a carrier solution are supplied to the lumen side (high pressure side, feed side) of the capillary ultrafiltration membrane and flow upward. Most of the carrier solution which contains dissolved solute gas, CO₂ in the present case, permeates the membrane to the permeate side (low pressure side, shell side), where the solution liberates dissolved gas to form a lean solution. The lean solution is circulated to the lumen side. This type of capillary membrane module was applied to the separation of CO₂ from model flue gases consisting of CO₂ and N₂. Monoethanolamine (MEA), diethanolamine (DEA) and 2-amino-2-methyl-1-propanol (AMP) were used as carriers or absorbents of CO₂. The feed side pressure was atmospheric and the permeate side was evacuated at about 10 kPa. CO₂ in the feed gas was successfully concentrated from 5–15% to more than 98%. The CO₂ permeance was as high as 2.7×10⁻⁴ mol m⁻² s⁻¹ kPa⁻¹ (8.0×10⁻⁴ cm³ cm⁻² s⁻¹ cmHg⁻¹) when the CO₂ mole fraction in the feed was 0.1 and temperature was 333 K. The selectivity of CO₂ over N₂ was in the range from 430 to 1790. The membrane was very stable over a discontinuous one-month testing period.     

Influence of the surface area of the support on the activity of gold catalysts for CO oxidation

In the preparation of 1% Au/TiO₂ catalysts supported on either Degussa P-25 or anatase (90 m² g⁻¹) by deposition–precipitation, the gold content passes through a maximum at about the isoelectric point (pH 6), but maximum specific rates occur at pH 8–9 because the Au particle size becomes smaller as the pH is further increased. The gold uptake increases with the surface area of the support (anatase, rutile, P-25) and is complete above 200 m² g⁻¹; adsorption of the gold precursor at pH 9 is shown to be equilibrium-limited. Highest activities are found with supports of 50 m² g⁻¹. Catalysts made with high-area anatase (240 or 305 m² g⁻¹) are least active but show least deactivation.With Au/SnO₂ catalysts, gold uptake does not depend on the area of the support, and is highest at pH 7–8; very active catalysts (T₅₀ = 230–238 K) are obtained using SnO₂ of 47 m² g⁻¹. Storing a catalyst at 258 K for 1 week dramatically improves its stability. Results for Au/CeO₂ and Au/ZrO₂ catalysts confirm that moderate support areas give the most active catalysts, and suggest that surface area is often more important than chemical composition.     

Enhancement of NaA zeolite membrane properties through organic cation addition

Thin NaA zeolite membranes, with uniform and small crystals, were prepared on the tubular -Al₂O₃ support by adding a small amount of tetramethylammonium hydroxide (TMAOH) in the clear synthesis solution. The as-synthesized NaA zeolite membranes were characterized by XRD and SEM. The permeation properties of the membranes were evaluated by pervaporation and gas permeation. The effects of TMAOH amount on membrane formation and permeation properties were investigated. By addition of suitable amount of TMAOH in the clear synthesis solution, the crystals size of NaA zeolite could be remarkably reduced from about 10 μm to 3–4 μm, and the membrane thickness correspondingly reduced from about 16 μm to 5 μm. The thinner membrane prepared by adding TMAOH in the clear synthesis solution, with uniform and small crystal, displayed higher perm-selective properties than that without adding TMAOH. For the as-synthesized NaA zeolite membrane prepared with adding suitable amount of TMAOH (x = 1), the separation factor (water/isopropanol) was 4700 and the flux was 1.67 kg/(m² h), which were higher than that without adding TMAOH of 339 and 1.08 kg/(m² h), respectively. The ideal separation factor of H₂/N₂ was 6.60, higher than that without adding TMAOH of 3.41.     

Preparation of 6FDA-based polyimide composite membrane by CVDP process

Preparation of polyimide composite membranes by a chemical vapor deposition and polymerization process (CVDP) was studied for the development of pervaporation or gas separation membranes. Hexafluoroisopropylidene-2,2-bis [phethalic acid anhydride] (6F-dianhydride) (6FDA) and 4,4′-diaminodiphenyl ether (ODA) were used as monomers and were simultaneously deposited on an asymmetric polyimide membrane in vacuum of 10⁻⁶ Torr. The deposited layer of the monomers was converted to polyimide by heating at 250°C at 3 h in an ordinary vacuum oven, and its separation performance for water-ethanol and CO₂−N₂ systems was characterized.     

Synthesis and oxygen transport characteristics of dense and porous cerium/gadolinium oxide materials: Interest in membrane reactors

Cerium/gadolinium oxide (CGO)-based ceramic ion conductive membranes (CICMs) have potential uses in catalytic membrane reactors (CMRs) and solid oxide fuel cells (SOFCs). A supercritical CO₂ aided sol–gel process allowed the synthesis of CGO materials with the composition Ce_0.9Gd_0.1O_1.95. The produced nanophase powders were non-agglomerated, with a controlled morphology, a high purity and a high specific surface area (>100 m²/g). The CGO cubic crystalline phase has been obtained at temperatures <300 °C, lower than those of conventional solid state chemistry routes. With respect to ionic oxygen transport, a high conductivity at intermediate temperature (2 × 10⁻² S cm⁻¹ at 600 °C), almost equivalent in dense and porous samples, has been obtained on sintered materials prepared from these powders. In relation to their porosity characteristics, a modelling approach successfully explained the high ionic oxygen transport of some specific porous samples. Future directions for preparing porous conductive ceramics well adapted to CMR or SOFC applications can be anticipated from this model.     

Synthesis and conductivity of proton-electrolyte membranes based on hybrid inorganic–organic copolymers

A class of new proton-electrolyte membranes (PEM) based on inorganic–organic copolymers were synthesized from 3-glycidoxypropyltrimethoxysilane (GPTS), sulfonated phenyltriethoxysilane (SPS), tetraethoxysilane (TEOS) and H₃PO₄. Their thermal stability, microstructure, and proton conductivity were investigated under the conditions for PEM fuel cell operation. TGA–DSC analysis indicated that these membranes are thermally stable up to 180 °C. Scanning electron microscope (SEM) micrographs show that the membranes are dense. A proton conductivity of 1.6×10⁻³ S/cm was observed at 100 °C in a dry atmosphere for a sample with 0.5 mol GPTS and 1 mol H₃PO₄ in 1 mol Si, representing the highest proton conductivity in anhydrous state among PEMs ever reported. In an environment with 15% relative humidity (RH), the proton conductivity increased to 3.6×10⁻² S/cm at 120 °C. The proton conductivity increases with H₃PO₄ contents and relative humidity. The hybrid inorganic–organic materials can be readily fabricated in membrane form with thickness as thin as 20 μm on porous electrodes; they have great potential to be used as the electrolytes for high-temperature PEM fuel cells.     

Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation

Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.     

The measurement of gas diffusivity in porous materials by temporal analysis of products (TAP)

The pulsing of argon in a temporal analysis of products (TAP) reactor and reactor modeling of the response curves were used to measure the effective intraparticle diffusivities in porous materials. The diffusivity that can be measured is limited: (1) at the low end by intraparticle diffusion being too slow such that just a small fraction of the pulse gets into the pores to give an indistinguishable tail, which only measures that the diffusivity is smaller than an upper limit and (2) at the high end by intraparticle diffusion being too fast such that it gives a constant concentration in the pores, which only measures that the diffusivity is larger than a lower limit. The limits and range are slightly different for different particle and bed dimensions. A 9 mm long packed bed has a sensitive range of about 300-fold where there are discernible changes in the normalized pulse shape due to diffusivity changes. If small particles of about 50 μm are used, the range is from 1 × 10⁻¹⁰ to 3 × 10⁻⁸ m²/s, and if large particles of about 500 μm are used, the range is from 2 × 10⁻⁹to 5 × 10⁻⁷ m²/s.