Purification of steryl esters from soybean oil deodorizer distillate

Soybean oil deodorizer distillate (SODD) contains steryl esters in addition to tocopherols and sterols. Tocopherols and sterols have been industrially purified from SODD but no purification process for steryl esters has been developed. SODD was efficiently separated to low b.p. substances (including tocopherols and sterols) and high b.p. substances (including 11.2 wt% DAG, 32.1 wt% TAG, and 45.4 wt% steryl esters) by molecular distillation. The high b.p. fraction is referred to as soybean oil deodorizer distillate steryl ester concentrate (SODDSEC). We attempted to purify steryl esters after a lipase-catalyzed hydrolysis of acylglycerols in SODDSEC. Screening of industrially available lipases indicated that Candida rugosa lipase was most effective. Based on the study of several factors affecting hydrolysis, the reaction conditions were determined as follows: ratio of SODDSEC/water, 1∶1 (w/w); lipase amount, 15 U/g reaction mixture; temperature, 30°C. When SODDSEC was agitated for 24 h under these conditions, acylglycerols were almost completely hydrolyzed and the content of steryl esters did not change. However, study with a mixture of steryl oleate/trilinolein (1∶1, w/w) indicated that about 20% of constituent FA in steryl esters were exchanged with constituent FA in acylglycerols. Steryl esters in the oil layer obtained by the SODDSEC treatment with lipase were successfully purified by molecular distillation (purity, 97.3%; recovery, 87.7%).     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.     

Production of structured lipids containing essential fatty acids by immobilizedRhizopus delemar lipase

An attempt was made to produce structured lipids containing essential fatty acid by acidolysis with 1,3-positional specificRhizopus delemar lipase. The lipase was immobilized on a ceramic carrier by coprecipitation with acetone and then was activated by shaking for 2 d at 30°C in a mixture of 5 g safflower or linseed oil, 10 g caprylic acid, 0.3 g water and 0.6 g of the immobilized enzyme. The activated enzyme was transferred into the same amount of oil/caprylic acid mixture without water, and the mixture was shaken under the same conditions as for the activation. By this reaction, 45–50 mol% of the fatty acids in oils were exchanged for caprylic acid, and the immobilized enzyme could be reused 45 and 55 times for safflower and linseed oils, respectively, without any significant loss of activity. The triglycerides were extracted withn-hexane after the acidolysis and then were allowed to react again with caprylic acid under the same conditions as mentioned above. When acidolysis was repeated three times with safflower oil as a starting material, the only products obtained were 1,3-capryloyl-2-linoleoylglycerol and 1,3-capryloyl-2-oleoyl-glycerol, with a ratio of 86∶14 (w/w). Equally, the products from linseed oil were 1,3-capryloyl-2-α-linolenoyl-glycerol, 1,3-caprylol-2-linoleoyl-glycerol, and 1,3-capryloyl-2-oleoly-glycerol (60∶22∶18, w/w/w). All fatty acids at the 1,3-positions in the original oils were exchanged for caprylic acid by the repeated acidolyses, and the positional specificity ofRhizopus lipase was also confirmed to be strict.     

Reverse osmosis separations of aldehydes,ketones, and ethers in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis data for a number of aldehyde, ketone, and ether solutes whose polar parameters Σσ* lie in the ranges of ?0.2 to 0.6, ?0.4 to 0.6, and ?0.49 to 0.6, respectively, have been analyzed. The results show that solute transport parameters can be expressed as a function of steric parameters ΣE_s only for ethers, polar parameter Σσ* only for aldehydes, and both ΣE_s and Σσ* for ketones. The numerical values of the functional proportionality constants ρ* and δ* associated with Σσ* and ΣE_s respectively, for the above class of solutes have been determined for operating pressures up to 500 psig, and a method of predicting solute separation from data on any reference solute only in each class has been established. The data on solute transport parameters for ethers, aldehydes, and ketones have been correlated with the corresponding data for sodium chloride through appropriate link constants. Analysis of data on mixed solute systems involving aldehydes and ketones show that the solutes behave independently in reverse osmosis.     

Decomposition of nitric oxide on metallosilicates under a large excess oxygen condition with coexistence of a low concentration cetane

Catalytic removal of NO was conducted under the condition of large excess O₂ by using different kinds of metallosilicates having MFI structure. With coexistence of a low concentration of cetane, H-Fe-silicate, which had both acidity and redox property, exhibited the maximum performance among the catalysts tested at a fairly lower temperature range, around 350 °C, and the NO was totally converted. The temperature dependence of NO conversion was consistently similar to that of cetane combustion.     

Production of MAG of CLA in a solvent-free system at low temperature with <Emphasis Type="Italic">Candida rugosa</Emphasis> lipase

We attempted to produce MAG of CLA through lipase-catalyzed esterification of a FFA mixture containing CLA (referred to as FFA-CLA) with glycerol. Screening of lipases showed that MAG-CLA was produced efficiently at 5°C with Penicillium camembertii, Rhizopus oryzae, and Candida rugosa lipases. Among them, C. rugosa lipase was selected because the lipase is widely used as a catalyst for oils and fats processing. The reaction was conducted with agitation of a 300-g mixture of FFA-CLA/glycerol (1∶5, mol/mol), a 200-U/g mixture of C. rugosa lipase, and 2% water. When the reaction was conducted at 30°C, the esterification scarcely proceeded, owing to inhibition of the reaction by glycerol. But the reaction at 5°C eliminated the inhibition and produced MAG efficiently: The degree of esterification reached 93.8% after 58 h, and MAG content in the reaction mixture was 88.4 wt%. To reduce the reaction time, the reactor was connected with a vacuum pump after 24 h, and the reaction was continued with dehydration at 5 mm Hg. The degree of esterification reached 94.7% after 24 h of dehydration (48 h in total), and MAG content increased to 93.0 wt%. Candida rugosa lipase acted a little more strongly on cis-9, trans-11 CLA than on trans-10,cis-12 CLA, but the contents of the two isomers in MAG obtained from a 48-h reaction were the same as the contents in FFA-CLA.     

LARCTMTPI Containing Pendant Phenoxy Moieties

The poly(keto-imide), LARC^TM-TPI, was developed in the late 1970's and has proven to be remarkable stable as a high temperature adhesives. Thermal aging results that were generated at both NASA Langley Research Center and at Boeing Aerospace Company proved this material to be stable in adhesive bond form for at least 60,000 hours at 232°C. A commercial form of LARC^TM-TPI was made available in the mid-to-late 1980's by Mitsui Toatsu Chemicals, Inc. (MTC). Since that time, MTC has optimized the process for manufacturing LARC^TM-TPI with the major improvements being in molecular weight control. Most recently, MTC synthesized a derivatized version of LARC^TM-TPI which contains pendant phenoxy moieties. This material is soluble in a number of organic solvents and it exhibits outstanding melt-flow properties which make it attractive as a hot-melt-processable polyimide adhesive. The synthesis and characterization of this novel material is the subject of this research paper.     

Specification of commercial reverse osmosis modules and predictability of their performance for water treatment applications

Techniques for specifying membranes in commercial modules and reverse osmosis systems involving such modules, and for predicting data on performance of the modules so specified are illustrated with particular reference to water treatment applications. Four commercial modules (Roga-4000, Westinghouse, Raypak and Du Pont-B9) were studied in. this work for such specification and prediction. Experimental reverse osmosis data using NaCl-H₂O feed solutions were used for obtaining data on membrane specifications. Equations of system analysis were used for prediction of data on module performance. Three sets of calculated data are reported for the operating pressure of 2758 kPa gauge (400 psig). The first set of data shows good agreement between calculated and experimental results on the performance of the modules with aqueous sucrose feed solutions. The second set of data shows the variations in solute separation and membrane productivity for each of the four- modules studied as functions of volumetric fraction product water recovery and membrane compaction for a 3000 ppm NaCl-H₂O feed solution. The third set of data shows the variations in solute separation as a function of solute transport parameter at different levels of mass transfer coefficient on the high pressure side of the membrane for very dilute aqueous feed solutions.     

Hydrothermal doping method for preparation of Cr-TiO2 photocatalysts with concentration gradient distribution of Cr

Cr³⁺-doped anatase titanium dioxide photocatalysts were prepared by the combination of sol–gel process with hydrothermal treatment. The samples were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area (S_BET), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was confirmed that Cr substitutes Ti⁴⁺ in TiO₂ lattice in trivalent ionic state, and the concentrations of dopants Cr³⁺ decrease from the exterior to the interior of doped TiO₂. The photocatalytic activity of Cr-TiO₂ was investigated for the photocatalytic degradation of XRG aqueous solution both under UV and visible light irradiation. Due to the excitation of 3d electron of Cr³⁺ to the conduction band of TiO₂, Cr-TiO₂ shows a good ability for absorbing the visible light to degrade XRG. Doping of chromium ions effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.15% and 0.2%, respectively. The special distribution of dopants Cr³⁺ seems having a good effect on enhancing the photocatalytic activity of Cr-TiO₂.     

Improved lipase-catalyzed incorporation of long-chain fatty acids into medium-chain triglycerides assisted by supercritical carbon dioxide extraction

Displacement of the equilibrium of the lipase-catalyzed interesterification between medium-chain triglyceride (MCT) and long-chain polyunsaturated fatty acid was accomplished by the removal of by-products with continuous supercritical carbon dioxide (SC−CO₂) extraction at 60°C and 100 kg/cm². The incorporation of eicosapentaenoic acid to MCT was appreciably improved by this method and was 1.3 times higher than that of the equilibrium state (47 wt%) that was obtained in a closed system. The immobilizedMucor miehei lipase was stable for more than 180 h in SC−CO₂ at 60°C and 100 kg/cm². Presented at ISF-JOCS World Congress, Tokyo, Japan, September 26–30, 1988.