Studies on the state of permeant in the membrane and its effect on pervaporation phenomena

Pervaporation experiments of pure water and 2-propanol through poly-dimethylsiloxane membranes were carried out in order to study the effect of the interaction between permeant and membrane material on pervaporation phenomena. From the effect of downstream pressure on the pervaporation rate, the saturation vapor pressure of water in the membrane was determined to be 2.799 × 10³ Pa (21.0 mmHg), which is the same as the literature value, whereas that of 2-propanol in the membrane was estimated to be 5.865 × 10³ Pa (44.0 mm Hg), which is 8.53 × 10² Pa (6.4 mmHg) higher than that of pure 2-propanol. In the differential scanning calorimetry analyses of permeants in the membrane, it was evident that the state of 2-propanol in the polydimethylsiloxane membrane was different from that of bulk 2-propanol. On the other hand, the state of water in the membrane was assigned to that of bulk water. Throughout the present study, it was observed that the interaction between permeant and membrane material plays an important role in determining pervaporation phenomena.     

Effects of membrane thickness and heat treatment on the gas transport properties of membranes based on P84 polyimide

P84 polyimide membranes with thicknesses ranging from 6 to 310 μm were successfully fabricated by spin coating. The glass transition temperature of the P84 powder was found to be 315°C using differential scanning calorimetry, whereas its decomposition temperature was 536°C using thermogravimetric analysis. Scanning electron microscopy was used to examine the morphology of the membranes. The permeability of single gas (He, N₂, O₂, and CO₂) and the ideal selectivity of gas pair (O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂), as a function of membrane thickness, were determined. The results showed that the permeability of a single gas increased with increasing membrane thickness, whereas the selectivity of a given gas pair was nearly independent of the membrane thickness. The average selectivity of O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂ were found to be 8.2, 10.0, 12.9, and 15.8, respectively. The effects of heat treatment on the membrane morphology and gas transport properties were investigated for three annealing temperatures, i.e., 80°C, 200°C, and 315°C. The membrane annealed at 315°C was cracked due to the stress sustained either during heating or cooling, thereby resulting in little or no selectivity. The permeabilities of P84‐118 membrane (118 μm thickness) annealed at 80°C were 16.2, 0.196, 1.20, and 2.01 Barrer for He, N₂, O₂, and CO₂, respectively. The permeabilities of P84‐118 membrane annealed at 200°C decreased by 9.75%, 47.96%, 25.83%, and 30.85% for He, N₂, O₂, and CO₂, respectively, as compared with those at 80°C, whereas the ideal selectivities increased by 42.65%, 30.52%, 32.85%, and 21.63% for O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of Isomeric Propanols on the Performances of Polyethersulfone Nanofiltration Membranes

Abstract

In this work, polyethersulfone (PES) asymmetric nanofiltration (NF) membranes were prepared by immersion precipitation phase inversion process. The casting solution contained N-methyl-2-pyrrolidone (NMP) as solvent, 1-propanol and 2-propanol as nonsolvent additives, and polyvinylpyrrolidone (PVP) as pore former additive. Water was used as a coagulant. The effects of the PVP content in the casting solution and the exposed time on the performances of the NF membranes were investigated. It was found that with the increase of PVP content, the pure water flux (PWF) increased to the largest value and then decreased. The rejection to PEG 1000 always decreased. The largest value (1281.40 kg · m^?2 · h^?1 · MPa^?1) of PWF appeared when the content of 1-propanol was 9 wt.%. However, when 2-propanol was added in the casting solution, the largest value of PWF was only 678.37 kg · m^?2 · h^?1 · MPa^?1 (the content of 2-propanol was 7 wt.% and other preparing conditions were unchanged). The results meant that both PWF and rejection of the membranes with 1-propanol as additive were higher than that of 2-propanol as additive. The possible reason was discussed from the viewpoint of the difference of solubility of propanols to PES and PVP.     

N-Alkylation of chitin and some characteristics of the novel derivatives

Summary Introduction of simple alkyl groups at the C-2 nitrogen of chitin and some properties of the resulting N-alkyl-chitins have been examined. Chitosan was fully deacetylated and treated with three kinds of aldehydes, formaldehyde, acetaldehyde, and pentanal. The Schiff bases of chitosan, whose extents of substitution were dependent on the amount of aldehydes, were reduced with sodium cyanoborohydride to N-alkylated chitosans. The N-alkyl-chitosans were then transformed into the corresponding N-alkyl-chitins by acetylation with acetic anhydride followed by transesterification to remove partly formed O-acetyl groups. The resulting N-methyl-, ethyl-, and pentyl-chitins were amorphous and showed improved affinity for organic solvents. Received: 13 December 2001/Revised version: 11 January 2002/Accepted: 17 January 2002     

Gas permselection properties in silicone-coated asymmetric polyethersulfone membranes

The gas permeation properties of H₂, He, CO₂, O₂, and N₂ through silicone-coated polyethersulfone (PESf) asymmetric hollow-fiber membranes with different structures were investigated as a function of pressure and temperature and compared with those of PESf dense membrane and silicone rubber (PDMS) membrane. The PESf asymmetric hollow-fiber membranes were prepared from spinning solutions containing N-methyl-2-pyrrolidone as a solvent, with ethanol, 1-propanol, or water as a nonsolvent-additive. Water was also used as both an internal and an external coagulant. A thin silicone rubber film was coated on the external surface of dried PESf hollow-fiber membranes. The apparent structure characteristics of the separation layer (thickness, porosity, and mean pore size) of the asymmetric membranes were determined by gas permeation method and their cross-section morphologies were examined with a scanning electron microscope. The results reveal that the gas pressure normalized fluxes of the five gases in the three silicone-coated PESf asymmetric membranes are nearly independent of pressure and did not exhibit the dual-mode behavior. The activation energies of permeation in the silicone-coated asymmetric membranes may be larger or smaller than those of PESf dense membrane, which is controlled by the membrane physical structure (skin layer and sublayer structure). Permselectivities for the gas pairs H₂/N₂, He/N₂, CO₂/N₂, and O₂/N₂ are also presented and their temperature dependency addressed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 837–846, 1997     

Direct and transfer hydrogenation of furfural over MOF-derived Pd-Cu@C catalysts

Owing to the self-reducing ability of palladium acetate in solutions, an ethanol solution containing Pd⁰ particles was prepared and coated in-situ into copper metal–organic framework (Cu-MOF), forming Pd@Cu-MOF in a coated structure. The Pd@Cu-MOF was reduced under N₂ or H₂ to form carbon-coated Pd-Cu@C. The pyrolysis and carbonization of Cu-MOF and the reduction of Cu²⁺ were studied. The Cu-MOF under either N₂ or H₂ was pyrolyzed and carbonized, but the Cu²⁺ reduction mechanisms were different. The high-temperature carbothermic reduction of Cu²⁺ under N₂ produced Cu⁰, but during low-temperature reduction under H₂, the reducing H₂ reduced Cu²⁺ to Cu⁰. Furfural hydrogenation experiments showed that compared with H₂, the Pd-Cu@C prepared under N₂ reduction displayed higher furfural hydrogenation activity. The catalytic activity of Pd-Cu@C prepared from in-situ Pd⁰ coating was higher than the Pd/Cu@C prepared from the impregnation method. With i-propanol as the solvent, the catalytic hydrogenation of furfural under H₂ consisted of direct catalytic hydrogenation with molecular hydrogen as the hydrogen source and catalytic transfer hydrogenation with i-propanol as the hydrogen donor. The catalytic activity of direct catalytic hydrogenation is higher than the catalytic transfer hydrogenation.     

Separation of VOCs from N2 using poly(ether block amide) membranes

This work deals with the separation of volatile organic compounds (VOCs) from nitrogen streams for organic vapour emission control by poly(ether block amide) membranes. As representative air pollutant VOCs, n‐pentane, n‐hexane, cyclohexane, n‐heptane, methanol, ethanol, n‐propanol, n‐butanol, acetone, dimethyl carbonate, and methyl tert‐butyl ether were used in this study. The separation of both binary VOC/N₂ and multicomponent VOCs/N₂ gas mixtures was carried out, and the membranes exhibited good separation performance. A VOC concentration of more than 90 mol% was achieved at a feed VOC concentration of 5 mol%. It was found that the permeances of the VOCs were mainly dominated by their solubilities in the membrane, whereas the permeance of N₂ was affected by the presence of the VOCs. The permeance of N₂ in the VOC/N₂ mixtures was shown to be higher than pure N₂ permeance due to membrane swelling induced by the VOCs dissolved in the membrane. Nevertheless, theVOC/N₂ selectivity increased with an increase in the feed VOC concentration. Among the VOCs studied, the membrane showed a higher permeance to alcohol VOCs than paraffin VOCs. The effects of feed VOC concentration, temperature, stage cut, and permeate pressure on the separation performance were investigated.     

TiO2 nanotube arrays annealed in CO exhibiting high performance for lithium ion intercalation

Anatase titania nanotube arrays were fabricated by means of anodization of Ti foil and annealed at 400 °C in respective CO and N₂ gases for 3 h. Electrochemical impendence spectroscopy study showed that CO annealed arrays possessed a noticeably lower charge-transfer resistance as compared with arrays annealed in N₂ gas under otherwise the same conditions. TiO₂ nanotube arrays annealed in CO possessed much improved lithium ion intercalation capacity and rate capability than N₂ annealed samples. At a high charge/discharge current density of 320 mA g⁻¹, the initial discharge capacity in CO annealed arrays was found to be as high as 223 mAh g⁻¹, 30% higher than N₂ annealed arrays, ∼164 mAh g⁻¹. After 50 charge/discharge cycles, the discharge capacity in CO annealed arrays remained at ∼179 mAh g⁻¹. The improved intercalation capacity and rate capability could be attributed to the presence of surface defects like Ti-C species and Ti³⁺ groups with oxygen vacancies, which not only improved the charge-transfer conductivity of the arrays but also possibly promoted phase transition.     

Construction of silicone with quaternized hydantoin-based N-chloramines on cotton with aid of supercritical interpenetration for antibacterial synergism

A silicone carrying combined functionalities of different mechanisms and physiochemical properties is synthesized as a strategy for faster and broader bacterial eliminations. Briefly, ring-opening alcoholysis of succinic anhydride with 2-dimethylaminoethanol and subsequent esterification of the alcoholysis product with 5-(4-hydroxyphenyl)imidazolidine-2,4-dione produced a structure with one tertiary amine and two hydantoinyl N H bonds. The tertiary amine was quaternized with 3-chloro-1-propanol whose O H was then alcoholyzed with Si H of poly(methylhydrosiloxane). The polymeric product was interpenetrated into cotton at 30 MPa and 50°C in supercritical CO₂ and treated with tert-butyl hypochlorite to chlorinate its hydantoinyl N H bonds, forming a 78 nm biocidal layer of silicone with quaternized hydantoin-based N-chloramines. Antibacterial tests showed that the quaternary ammonium salt and two hydantoin-based N-chloramines act synergistically due to their complementary features, killing both Staphylococcus aureus and Escherichia coli much more efficiently than each functionality. More importantly, the ratio of N-chloramine to quaternary ammonium salt of 2:1 herein also provided higher efficacy than a reported counterpart with a 1:1 ratio. Biocidability of the modified cotton had promising stability and rechargeability, which indicates that supercritical interpenetration produced a durable interfacial layer without the necessity of chemical bonding.     

Spectroscopic and Kinetic Analysis of a New Low-Temperature Methanol Synthesis Reaction

The spectroscopy and kinetics of a new low-temperature methanol synthesis method were studied by using in situ DRIFTS on Cu/ZnO catalysts from syngas (CO/CO₂/H₂) using alcohol promoters. The adsorbed formate species easily reacted with ethanol or 2-propanol at 443 K and atmospheric pressure, and the reaction rate with 2-propanol was faster than that with ethanol. Alkyl formate was easily reduced to form methanol at 443 K and 1.0 MPa, and the hydrogenation rate of 2-propyl formate was found to be faster than that of ethyl formate. 2-Propanol used as promoter exhibited a higher activity than ethanol in the reaction of the low-temperature methanol synthesis.     

Separation of CO2 by 2-amino-2-methyl-1-propanol aqueous solution in microporous hydrophobie hollow fiber contained liquid membrane

The absorption of CO₂ from a mixture of CO₂/N₂ gas was carried out using a flat-stirred vessel and the polytetrafluoroethylene hollow fiber contained aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The reaction of CO₂ with AMP was confirmed to be a second order reversible reaction with fast-reaction region. The mass transfer resistance in the membrane side obtained from the comparison of the measured absorption rates of CO₂ in a hollow fiber contained liquid membrane with a flat-stirred vessel corresponded to about 90% of overall-mass-transfer resistance. The mass transfer coefficient of hollow fiber phase could be evaluated, which was independent of CO₂ loading.     

Effect of doping treatment on gas transport properties and on separation factors of polyaniline memebranes

Gas permeation experiments of H₂, O₂, CO₂, N₂, and CH₂ were carried out with freestanding films of the conjugated polymer polyaniline (PANi). At first annealed to remove residual solvent, PANi membranes were doped (i.e., protonated) in a strongly acidic medium (HCl 4M), undoped in a basic medium (NH₄OH 1M), and redoped in a slightly acidic medium (HCl 10^?2M). Protonation and deprotonation kinetics were studied by elementary analysis Gas permeation experiments were performed with the annealed, doped, undoped, and redoped PANi films. The gas transport mechanism was clearly influenced by the diffusivity factor and it obeyed a Fickian diffusion model. From the variations in permeability coefficients with the doping treatment, gases could be divided in two subgroups comprising H₂, O₂, and CO₂ on one hand and N₂ and CH₄ on the other. After the doping–undoping–redoping process, gas fluxes were increased by 15% for the smaller gases and were decreased by 45% for the larger gases. As a consequence gas separation factors were approximately doubled for a gas pair involving the two subgroups and these were unchanged for a gas pair involving only one subgroup. The highest O₂/N₂ and CO₂/CH₄ selectivity coefficients were, respectively, equal to 14 and 78. © 1995 John Wiley & Sons, Inc.     

Permeability of phenol through cellulose acetate membranes by reverse osmosis in various alcoholic systems

Reverse osmosis separation of phenol in various alcoholic solutions using porous cellulose acetate membranes was investigated. The permeation behavior of phenol was measured for cellulose acetate membranes having various pore size distributions which were prepared by annealing at four different temperatures. Some differences were found between the aqueous and the alcoholic solutions in solute permeabilities and product rates. Membranes annealed at 90°C showed higher permselectivity than membranes annealed at lower temperatures. The pore character was classified into two types according to the relation of the product rate of 1-propanol and that of water. It was found in a series of alcoholic solutions that the permeability of phenol, the product rate, and the apparent partition coefficient are closely related to the carbon number of the alcohols, but the values of J_v × η (ca. 1.25 × 10^?4 poise·m³/m²·day) and of the permselectivity coefficient (ca. 0.83) remain constant. The result was analyzed by using the three-dimensional solubility parameter to obtain some information for the partition mechanism of solutes in aqueous and alcoholic solutions.     

Entanglement network of chitin and chitosan in ionic liquid solutions

Concentrated solutions of a chitin from squid pens and of two commercial samples of chitosan were successfully prepared by using an ionic liquid 1‐butyl‐3‐methylimidazolium acetate as a solvent. The dynamic viscoelasticity data for the solutions exhibited rubbery plateaus, indicating the existence of entanglement network of chitin and chitosan in the solutions. To characterize the network, the values of the molecular weight between entanglements (M_e) for chitin and chitosan in the solutions were determined from the plateau moduli. Then the values of M_e in the molten state (M_e,melt), a material constant reflecting the inherent nature of polymer species, for chitin and chitosan were estimated to be 1.7 × 10³ and 3.0 × 10³, respectively. It was found that there was a significant difference in M_e,melt between chitin and chitosan. Compared with other polysaccharides such as cellulose and agarose in terms of the number of monosaccharide units between entanglements (N_unit), chitin had significantly smaller N_unit of 8, while chitosan had equivalent N_unit of 19. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2439–2443, 2013     

Regioselective introduction of β-galactoside branches into chitosan and chitin

β-d-Galactoside branches have been introduced into chitosan and chitin regioselectively through a series of controlled modification reactions based on N-phthaloyl-chitosan. The glycosylation reaction between a chitosan derivative having a reactive group only at C-6 and an orthoester of d-galactose proceeded efficiently to give a protected product with a degree of substitution up to about 0.5. Deprotection gave a branched chitosan, and the subsequent N-acetylation afforded a branched chitin. Unlike chitosan and chitin, the resulting nonnatural branched polysaccharides were characterized by high affinity for solvents and readily soluble in neutral water. Furthermore, branched chitin was easily degraded by lysozyme. Received: 31 July 1997/Revised: 2 September 1997/Accepted: 19 September 1997     

Water–alcohol separation by pervaporation through poly(amide-sulfonamide)s (PASAs) membranes

Pervaporation membranes derived from seven homopolymers of poly(amide-sulfonamide)s (PASAs) were prepared by casting 10–17% polymer solutions of N,N-dimethylacetamide. The membranes were characterized by sorption experiments, scanning electron microscope, and wide-angle X-ray diffraction. During the pervaporation of 90 wt % aqueous solution of methanol, ethanol, 1-propanol, and 2-propanol, all membranes were preferentially permeable to water, and their separation factors were mainly dependent on the molecular weight of the solvent. The exact structure of the PASAs had a profound effect on their pervaporation characteristics. Polymeric membrane based on N,N′-bis(4-aminophenylsulfonyl)-1,3-diaminopropane and isophthaloyl chloride exhibited the best selectivity factor of 1984 for a 10 : 90 (by weight) mixture of water/ethanol at 20°C. However, the permeation rates of all materials for dehydration of 90 wt % ethanol were slow in a range of 6.6–34.4 g m⁻² h⁻¹. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1113–1119, 1997     

A Double Prodrug with Improved Membrane Permeability over the Parent Chelator HBED Provides Superior Cytoprotection against Hydrogen Peroxide

The clinical use of N,N′‐bis(2‐hydroxybenzyl)ethylenediamine‐N,N′‐diacetic acid (HBED) has been hindered by its lack of bioavailability. N,N′‐bis(2‐boronic pinacol ester benzyl)ethylenediamine‐N,N′‐diacetic acid methyl, ethyl, and isopropyl esters 7 a – c , respectively, and their dimesylate salts 8 a – c , are double prodrugs that mask the two phenolate and two carboxylate donors of HBED as boronic esters and carboxylate esters, respectively. Their activation by chemical hydrolysis and oxidation, their passive diffusivity, and their cytoprotective capabilities have been investigated here. 8 a – c hydrolyzed in minimum essential medium at 37 °C with half‐lives of 0.69, 0.81, and 2.28 h, respectively. The intermediate formed, 9 [N,N′‐bis(2‐boronic acid benzyl)ethylenediamine‐N,N′‐diacetic acid], then underwent oxidative deboronation by H₂O₂ to give HBED (k=1.82 m ^?1 min^?1). Solubility measurements in mineral oil and in phosphate buffer indicated that 7 a had a better balance between lipid and aqueous solubilities than did HBED. 7 a was also able to passively diffuse across a lipid‐like silicone membrane (log flux=?0.36), whereas HBED‐HCl was not. 8 c provided better protection to retinal cells than did HBED against a lethal dose of H₂O₂ (84 % vs. 28 % protection, respectively, at 44 μm ). These results suggest that the double prodrugs have better membrane permeability than does HBED, and therefore could be therapeutically useful for improving the delivery of HBED.     

Tailoring the bandgap of N-rich graphitic carbon nitride for enhanced photocatalytic activity

Nitrogen - rich graphitic carbon nitride (Ng-C₃N₄) with improved photocatalytic activity was engineered using a facile post-annealing treatment of pristine g-C₃N₄ in N₂ atmosphere. The thermal annealing did not modify the crystal structure, vibrational modes, or morphology of the N-rich g-C₃N₄ (Ng-C₃N₄). However, it decreased the crystallinity by broadening the dominant X-ray diffraction (XRD) peak and increased the surface area and mesoporous nature because of the formation of carbon vacancies. Diffuse reflectance spectroscopy indicated that the bandgap of the annealed Ng-C₃N₄ decreased from 2.82 to 2.77 eV compared to pristine g-C₃N₄. The increase of nitrogen content in the annealed Ng-C₃N₄ was quantified by X-ray photoelectron spectroscopy (XPS), which was also used to examine the formation of carbon vacancies. Photocurrent and electrochemical impedance spectroscopy measurements showed that the annealed Ng-C₃N₄ had higher light absorption capacity than the pristine g-C₃N₄. The photocatalytic performance of the samples was investigated for the degradation of crystal violet (CV) under ultra-violet light irradiation. The annealed Ng-C₃N₄ sample exhibited superior photodegradation of CV over pristine g-C₃N₄.     

In vitro comparative hemostatic studies of chitin,chitosan, and their derivatives

The effects of chitin, chitosan, and their derivatives on in vitro human blood coagulation and platelet activation were comparatively studied. The coagulation was assessed by the measure of the whole blood clotting time (WHBCT) and plasma recalcification time (PRT). The tested materials were chitin, chitosan, partially N‐acetylated chitosan (PNAC), N,O‐carboxymethylchitosan (NOCC), N‐sulfated chitosan, N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride, and SPONGOSTAN® standard (a positive control). The results revealed that the WHBCTs of whole blood mixed with chitin, chitosan, NOCC, or SPONGOSTAN® standard were significantly decreased with respect to that of the pure whole blood (a blank control) (P < 0.05), while the WHBCT value of whole blood mixed with PNAC was not significantly reduced. However, the presence of PNAC significantly lowered the PRT value, similar to the addition of chitin, NOCC, or SPONGOSTAN® standard. Chitosan was found to reduce PRT, but not significantly. In the platelet adhesion and activation studies, the morphology of platelets adherent to the film surfaces of tested materials was examined using a scanning electron microscopic technique. Because of their effective coagulation activites, chitosan, PNAC, and NOCC were further evaluated to determine how platelets behaved when in contact with these film samples for given periods. It was found that NOCC activated platelets most effectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 445–451, 2006     

Alkylation of phenol with 1-propanol and 2-propanol over catalysts derived from hydrotalcite-like anionic clays

Vapour phase alkylation of phenol with 1-propanol and 2-propanol was carried out in a fixed-bed flow reactor over calcined magnesium aluminium hydrotalcites (MgAl-CHT) with Mg/Al atomic ratios 2, 3 and 4. MgAl 3.0-CHT showed higher phenol conversion (80% at 350C, in the alkylation of phenol with 1-propanol. Both O- and C-alkylations were found to be taking place without any skeletal isomerization of the propyl moiety, suggesting an S_N2 type mechanism. Isomorphous substitution of Mg²⁺ by Cu²⁺ or Ni²⁺ in the hydrotalcite framework resulted in the predominant C-alkylation to give 2-n-propylphenol (60–70%) with nearly 40–50% phenol conversion at 350C. When 2-propanol was used as an alkylating agent, the phenol conversion decreased over all these catalysts and the alkylation was noticed exclusively at C-centers. Comparison of the product selectivity at constant phenol conversion revealed that CuAl 3.0-CHT is more selective for 2-n-propylphenol and 2-isopropylphenol in the reaction of phenol with 1-propanol and 2-propanol respectively. The participation of a pair of acid-base sites in the calcined hydrotalcites for the alkylation reaction has been proposed. The acid-base properties of these catalysts have been examined by the decomposition of cyclohexanol as a test reaction. Analysis of the spent catalysts revealed that Cu²⁺ in CuO gets reduced into Cu¹⁺ and metallic copper during the reaction in the case of CuAl-CHT, while MgO and NiO phases of MgAl-CHT and NiAl-CHT are retained.