The partial oxidation of ethane to acetaldehyde

The mixed oxide (B---P---O) prepared from H₃BO₃ and P₂O₅ was modified to a selective catalyst (B---P---O(S)) to the formation of CH₃CHO after prolonged treatment in a gas mixture of reactants. The contribution of gas-phase chain reactionsto the catalytic oxidations of C₂H₆ on the B---P---O(S) could be neglected. The catalytic active species on the B---P---O(S) was suggested to be a highly dispersed boron oxide supported on BPO₄ crystals. The mixed oxide prepared from BPO₄, H₃BO₃(7atom%), and P₂O₅(3atom%) showed the highest yield of CH₃CHO.     

Studies on syntheses and permeabilities of special polymer membranes. X. Effects of conditions of membrane preparation on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The effects of casting solvents, dissolution temperature of casting solution, and pH and temperature of gelation solution, etc. on the permeation characteristics of cellulose acetate membranes in the separation of polymers from their aqueous solutions were investigated, using aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) as feed. The permeation characteristics were influenced significantly by the conditions of membrane preparation and of the permeation. It was found that a concentration polarization at the membrane surface occurred with poly(vinyl alcohol) molecules, but it was very small with poly(ethylene glycol). The above results were discussed in detail from points of view of structure of the resulting membranes and the interactions between the solvent, the solute in the feed and the cellulose acetate molecules.     

Studies on syntheses and permeabilities of special polymer membranes. III. Permeation of aqueous alcohol solutions and binary organic liquid mixtures through alkali bridged poly(vinyl alcohol) membranes

The preparation conditions of water insoluble poly(vinyl alcohol) membranes were investigated using three kinds of monovalent alkali metal compounds, namely, lithium hydroxide, sodium hydroxide, and potassium hydroxide. The mechanism for the formation of water insoluble membranes is discussed. The permeabilities of pure alcohols were improved by adding ethylene glycol to the casting solutions and they depended upon the radii of alkali metal ions and the density of locations bridged with these ions. The permeation and separation characteristics of three different alcohol/water systems and three different alcohol/benzene systems through alkali bridged poly(vinyl alcohol) membranes were studied by changing the feed composition of the binary mixtures. In alcohol/water solutions, the depression of permeation depended upon the compaction of membrane under pressure. The permeation rate of water/lower alcohol solution was faster than that of water/higher alcohol solution in all feed compositions. Separation of water/alcohol at given water contents increased with an increase in the molecular length of the alcohols. In the three different alcohol/benzene systems, the permeation rates increased with an increase in the alcohol fraction in feed, and the permeation rate of benzene/lower alcohol mixture was faster than that of benzene/higher alcohol mixture in all feed compositions. Separation of benzene/alcohol mixtures at given benzene contents decreased with an increase in the molecular length of alcohols. These phenomena are discussed from the standpoint of the molecular size, the molecular shape, and the physicochemical natures of the permeating species and the polymer membrane.     

Characteristics of permeation and separation of aqueous alcoholic solutions through a poly[bis(2,2,2-trifluoroethoxy)phosphazene] membrane by evapomeation and pervaporation

The characteristics of permeation and separation for aqueous solutions of methanol and ethanol through a poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PBTFP) membrane were studied by pervaporation and evapomeation. In pervaporation technique, methanol was preferentially permeated in all of the feed solution compositions and ethanol was permeated in lower ethanol concentrations of the feed solution. Water was predominantly permeated from the feed solutions with higher ethanol concentration. In evapomeation technique, water was selectively permeated in both all of the feed vapor compositions for aqueous methanol and ethanol solutions. These different permselectivities depended on the feed composition and the membrane permeation technique and could be discussed by a difference in the mechanisms of permeation and separation. It was found that the permeation rate was influenced remarkably by the degree of swelling of the PBTFP membrane and the permselectivity for water of aqueous alcoholic solutions was enhanced by an increasing degree of swelling of the membrane. When the degree of swelling of the membrane with rising permeation temperature was small, both the permeation rate and permselectivity for alcohol in pervaporation and evapomeation increased with the permeation temperature. The above results are discussed considering the PBTFP membrane structure in evapomeation and pervaporation.     

Studies on syntheses and permeabilities of special polymer membranes: 50. Transport of metal ions against their concentration gradient through water-insoluble poly(styrene sulphonic acid) membrane

Water-insoluble cation exchange membranes were prepared by heat treating membranes made of poly(styrene sulphonic acid) and poly(vinyl alcohol). Transport of metal ions through the above cation exchange membrane against their concentration gradient was investigated under various conditions. The transport in this system, where one side of the membrane in a diaphragm cell was acidic and the other alkaline, was influenced significantly by the initial H⁺ ion concentration on the acidic side. The selectivity of metal ions in diffusive transport depended on the size of their hydrated ions and that in transport against their concentration gradient was due to the affinity between the metal ions and the carrier fixed to the membrane.     

Pervaporation characteristics of methyl methacrylate–methacrylic acid copolymer membranes ionically crosslinked with metal ions for a benzene/cyclohexane mixture

Methyl methacrylate–methacrylic acid copolymer (MMA–MAA) membranes ionically crosslinked with Fe³⁺ and Co²⁺ ions (MMA–MAA–Fe³⁺ and –Co²⁺) were prepared, and characteristics of permeation and separation for a benzene/cyclohexane mixture of 50 wt % benzene through these membranes in pervaporation (PV) were studied. Although the introduction of the metal ions to the MMA–MAA membrane enhanced both benzene permselectivity and permeability for a benzene/cyclohexane mixture, the PV characteristics between the MMA–MAA–Fe³⁺ and –Co²⁺ membranes were significantly different. The difference in the PV characteristics between these membranes was strongly governed by the difference of these membrane structures based on the glass transition temperature, contact angle to methylene iodide, degree of swelling, and mixture composition absorbed in the membrane, and so on. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 233–241, 1999     

Studies on syntheses and permeabilities of special polymer membranes. XIV. Permeation characteristics of modified nylon 12 membranes

The permeation characteristics and the burst strength of nylon 12 membranes treated with heat in various solutions such as aqueous solutions of formic acid, formic acid/formalin, and sodium hydroxide/ formalin were investigated under various conditions. They were significantly influenced by the treatment solution, temperature and time, and the concentration of acid and alkali in the treatment solution. In particular, nylon 12 membranes treated with formic acid/formalin remarkably improved the permeation characteristics and the burst strength. These phenomena were discussed from the standpoint of the effective pore size and pore number in the membrane, and the form and aggregation of polymer molecules forming the membrane.     

Studies on syntheses and permeabilities of special polymer membranes. 25. Effects of membrane preparation method on structure and permeation characteristics of poly(vinylidene fluoride) membranes

The permeation characteristics and the formation mechanisms of poly(vinylidene fluoride) (PVF₂) membranes were investigated by changing the casting solvent and the exposure period in the preparation conditions of the membranes. Changes of the microporous structure of the resulting membranes with the exposure period are dependent on differences in forming coacervated droplets based on phase separation. Changes of the permeation characteristics and the formation of coacervation by changing the combination of the mixed solvents are related to differences of the form of PVF₂ molecules in the casting solution, to differences of the formation of surface layer with the evaporation of a low and a high boiling point solvent, and to differences of the hygroscopicity of the high boiling point solvent.     

Studies on syntheses and permeabilities of special polymer membranes. VI. Permeation characteristics of cellulose nitrate membranes and cellulose membranes

The permeation characteristics of cellulose nitrate membranes and cellulose membranes were investigated using aqueous solutions of poly(ethylene glycol) as feed. To gain cellulose membranes the nitro groups in cellulose nitrate were converted to hydroxyl groups. It was found that cellulose nitrate membranes separate poly(ethylene glycol) 6000 but not any cellulose membrane did separate poly(ethylene glycol) 20 000.