Phase equilibrium data pertaining to the extraction of cottonseed oil with ethanol and 2-propanol

Summary Basic phase relation data have been obtained relative to the extraction of cottonseed oil with ethanol and 2-propanol, especially as affected by water in the solvent. Mutual solubility diagrams have been constructed for cottonseed oil with ethanol and 2-propanol of various aqueous concentrations. Tie-line data at 30° C. have been obtained for the ternary ethanol-cotton-seed oil-water and 2-propanol-cottonseed oil-water systems. These combined data will be of assistance in the selection of the most desirable temperatures and moisture concentrations in the solvent extraction of cottonseed with these alcohols. Comparison with results previously published for soybean oil suggests that the mutual solubility data for cottonseed oil and aqueous ethanols are applicable to other vegetable oils over a wide range of iodine values. In general, the results indicate that 2-propanol is the more desirable solvent since complete miscibility with the oil can be attained at temperatures below its normal boiling point even at moisture contents as high as 10% by weight whereas ethanol can tolerate only about 1.5% of water. High moisture contents result in more effective separation of the oil from the solvent when the miscella is cooled after extraction. Constant boiling aqueous ethanol and 2-propanol present the disadvantage of requiring greater than atmospheric pressure during extraction in order to attain complete miscibility with the oil. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Transesterification of phytosterol and edible oil by lipase powder at high temperature

Phytosterol, which is hardly soluble in edible oil, was solubilized at a high concentration by converting it to FA esters by lipase-catalyzed transesterification at temperatures higher than 100°C using powdered Lipase QLM (Meito Sangyo Co., Ltd., Nagoya, Japan). Transesterification was conducted, in sunflower oil containing 10% phytosterol, without adding water or solvent, at 100°C. The conversion rate was 97.1% after 7 h of reaction. The effect of temperature on the conversion rate was also examined. Maximum enzyme activity occurred in the 100–120°C range, and 20% of the maximum activity was retained even at 130°C. When the lipase was recovered by filtration and recycled for repeated reactions at 90°C, the half-life of lipase activity was 260 h. Thus, edible oils with nutritional value could be produced by blending the phytosterol-containing sunflower oil into other edible oils.     

Alcoholic extraction of vegetable oils. Part IV. Solubilities of vegetable oils in aqueous 2-propanol

Summary Solubilities of 14 vegetable oils in four different concentrations of aqueous 2-propanol at various temperatures were determined by a direct and simple method. Comprehensive solubility data of these oils and the critical solution temperatureversus 2-propanol composition data are presented in tabular form. Solubility of each oil in aqueous 2-propanol increases with temperature until the critical solution temperature is reached, at and above which oil and the solvent are miscible in all proportions. Further the critical solution temperatures of all the oils with aqueous 2-propanol solutions increased with the increase in water content of 2-propanol solutions. There appears to be a general relation between fatty acid contents of the oils and critical solution temperatures which needs further study. Presented at the 30th fall meeting, American Oil Chemists' Society, September 24–26, 1956, Chicago, Ill.     

Optimization of Deodorization Design for Four Different Kinds of Vegetable Oil in Industrial Trial to Reduce Thermal Deterioration of Product

Trans fatty acids (TFA) have been shown to be associated with various health disorders. Due to thermal stress, one major source of dietary TFA is high-temperature deodorization of vegetable oils. In this study, precision minimal deodorization was proposed to obtain healthier “zero-TFA” vegetable oils (TFA ≤0.3%). By optimizing temperatures for different deodorizers, dual columns with dual temperatures (DCDT) deodorizers were proposed, transformed, and industrially implemented among dozens of plants. The deodorization temperatures were optimized and customized, respectively, for four kinds of vegetable oil (soybean oil and rapeseed oil: tray column 205 °C and packed column 225 °C, maize oil and sunflower seed oil: tray column 210 °C and packed column 230 °C). Industrial trials showed that all four kinds of oils can achieve “zero-TFA” by DCDT deodorization at the customized mild temperatures, and meanwhile oil physicochemical qualities and shelf-life stabilities were compared with corresponding conventional refining oils. The initial free fatty acid and color were a little higher than that of conventional refining oils, but no significant differences were shown in change trends of these physicochemical indexes during the shelf life, which indicated a good and stable oil quality of “zero-TFA” oils for future industrial productions and sales.     

异烟酸乙酯的相转移催化合成

以 BTEAC(苄基三乙基氯化铵 )为相转移催化剂合成了异烟酸乙酯。无水乙醇既为溶剂又为反应物 ,所以固定无水乙醇与异烟酸的比例为 1∶ 1 7(摩尔比 ) ,即异烟酸 4.9g( 0 .0 4 mol) ,无水乙醇 40 m L,使无水乙醇大大过量。利用正交实验考察浓 98%H2 SO4(质量分数 ,下同 )用量 ,BTEAC用量 ,反应液最终温度对产率的影响。实验确定了最佳反应条件 :H2 SO45 .5 g,相转移催化剂 0 .3g,最终反应温度 1 0 5°C,收率 82 .6%。在其他条件相同而不加相转移催化剂时收率只有44.6%,实验结果表明相转移催化剂的使用可以提高异烟酸乙酯的产率。     

Factors affecting the solubility of gypsum: II. Effect of sodium hydroxide under various conditions

A quantitative estimation of the effect of sodium hydroxide on the solubility of gypsum in the presence of lime at 30, 60 and 100°C is given. At 30°C the solubility of gypsum was promoted by a 0.0146M solution of sodium hydroxide which at a concentration as low as 0.0029M raised the sulphate ion concentration at 60 and 100°C. At the three temperatures studied the solubility curves of gypsum first rose slowly then more rapidly around 0.02 to 0.08M NaOH. In the range 0.08 to 1M NaOH solution, a constant value of the sulphate ion concentration was measured which corresponded to the complete dissolution of gypsum, even in the presence of lime. The solubility curve of gypsum was lowered slightly at 30°C in a supersaturated lime solution and was depressed by concentrations lower than or equal to 0.02M NaOH solutions at 60 and 100°C.     

Factors affecting the solubility of gypsum. The effect of lime and temperature in different media

The effect of lime on the solubility of gypsum in water and in sodium hydroxide solution at 30, 60 and 100°C has been studied turbidimetrically and by means of X-ray diffraction analysis. Lime depressed the solubility of gypsum in water only slightly at 30°C and a rise of temperature minimised its effect until its complete elimination. In the absence of alkali the minimum sulphate ion concentration in a supersaturated lime solution and at temperatures in the range 30–100°C is about 1.2gdm⁻³. In sodium hydroxide solution neither lime nor temperature played a significant role and the solubility of gypsum was clearly promoted. At temperatures in the range 30–100°C, 0.5g of gypsum dissolved in 100cm³ of 0.2MNaOH solution.     

Studies on the alcoholysis of some seed oils

The effects of time and temperature on the alcoholysis of rubber seed, melon seed, linseed, and soyabean oils have been studied. The following temperatures were investigated: 200, 220, 245, and 260°C. Litharge (PbO) was used as the alcoholysis catalyst. The optimum alcoholysis temperature was found to be 245 ± 2 °C for each of the oils. At lower alcoholysis temperatures (<245°C), there is the preferential alcoholysis of seed oils derived from unsaturated acid; and the general alcoholysis rates were found to be in the following order: linseed oil ≈ rubber seed oil ≥ soyabean oil ≈ melon seed oil. The alcohol‐solubility of the oils is generally observed to begin at 42–45% conversion of oils to monoglycerides. The α‐monoglyceride contents of the alcoholysis mixtures of rubber seed and linseed oils were generally similar at methanol tolerance, and higher than those of melon seed and soyabean oils. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1826–1832, 2000     

Poly(methyl methacrylate-co-acrylonitrile)

Stable macroradicals of methyl methacrylate were prepared by the azobisisobutyronitrile-initiated polymerization of methyl methacrylate in hexane whose solubility parameter value (δ) differed from that of the macroradical by more than 1.8 hildebrand units and in 1-propanol at temperatures below its theta temperature (84.5°C). The rates of heterogeneous polymerization in hexane and 1-propanol were much faster than that of the homogeneous polymerization in benzene. Stable macroradicals were not obtained in benzene which was a good solvent nor at temperatures above the glass transition temperature (T_t) of the macroradicals. Thus, stable macroradicals of butyl methacrylate (T_g20°C) and and methyl acrylate (T_g3°C) were not obtained at a polymerization temperature of 50°C. Good yields of block copolymers of methyl methacrylate and acrylonitrile were obtained by the addition of acrylonitrile to the methyl methacrylate macroradical in methanol, ethanol, 1-propanol and hexane at 50°C. The rate of formation of the block copolymer decreased in these poor solvents as the differences between the solubility parameter of the solvent and macroradical increased.The block copolymer samples prepared at temperatures of 50°C and above were dissolved in benzene which is a non-solvent for acrylonitrile homopolymer, but is a good solvent for poly(methyl methacrylate) and the block copolymer. The presence of acrylonitrile and methyl methacrylate in the benzene-soluble macromolecule was demonstrated by pyrolysis gas chromatography, infra-red spectroscopy and differential thermal analysis.     

Formation of headspace volatiles by thermal decomposition of oxidized fish oilsvs. oxidized vegetable oils

To understand the reasons for differences in oxidative stability among edible oils, the temperature dependence was investigated for the development of volatile lipid oxidation products in fish oils and in vegetable oils. A rapid headspace capillary gas chromatographic method was developed to determine volatile oxidation products of omega-6 (n-6) polyunsaturated fats (pentane and hexanal) and omega-3 (n-3) polyunsaturated fats (propanal) at different decomposition temperatures. Headspace gas chromatographic analyses of partially oxidized menhaden, bonita and sardine oils could be performed at 40°C, whereas soybean, canola, safflower, high-oleic sunflower and high-oleic safflower oils required temperatures greater than 100°C. Volatile formation by thermal decomposition of oxidized oils had lower apparent activation energies in fish oils than in vegetable oils, and significantly higher apparent activation energies in high-oleic oils than in polyunsaturated oils. The activation energy data on headspace volatiles provided another dimension toward a better understanding of the thermal stability of flavor precursors in unsaturated fish and vegetable oils. Presented at the ISF/AOCS joint meeting, Toronto, Canada, May 10–14, 1992.     

The Role of Water in Protection Against Thermal Deterioration of Liquid Margarine

The thermal stability of liquid margarine and vegetable oils was investigated by measuring the oxidative stability index (OSI) at temperatures ranging from 90 to 180 °C, whereas total polar compounds (TPC) and tocopherols (vitamin E) were measured during heating at 180 °C in frying trays. Results showed that the OSI of liquid margarine was in the same range as the OSI of vegetable oils at lower temperatures, but at 160 and 180 °C, liquid margarine had significantly higher thermal stability, close to that observed for hard margarine and butter. The increased stability was confirmed by lower levels of TPC and a smaller relative reduction in vitamin E content during heating. Variations between different vegetable oils could partly be explained by differences in degree of saturation and level of vitamin E, with high oleic sunflower oil being the most stable oil at all temperatures. The water in liquid margarine vaporized within 1.5 min at 160 °C, and it is hypothesized that volatile pro‐oxidants are removed with the water, inducing a delay in deterioration. The results indicate a role for water in preventing lipid oxidation and decomposition in fat emulsion products at 160–180 °C, suggesting that liquid margarine, low in saturated fat, may be the healthier and preferable alternative for pan‐frying compared to other liquid vegetable oils.     

Noncatalytic alcoholysis kinetics of soybean oil

Reaction kinetics for the alcoholysis of soybean oil with methanol, ethanol, and isopropanol were evaluated in the absence of catalyst. Metal reactor surfaces catalyzed these reactions, so the reactions were conducted in glass capillary tubes at 120, 150, and 180°C. The reactivity of the alcohols increased with decreasing carbon number. Higher temperatures promoted faster reactions. Higher alcohol stoichiometries did not significantly increase reaction rates; this was attributed to the limited solubility of the alcohol in the soybean oil. At less than 20% conversion, the solubility of the alcohol in the oil phase continuously increased, resulting in increased reaction rates. At approximately 20% conversion, the reaction systems became homogeneous until a glycerine phase was formed at high conversions. In addition to their fundamental value, these data provided a basis on which catalytic reactions can be investigated between 100 and 200°C.     

Bland undenatured soybean flakes by alcohol washing and flash desolventizing

The conditions for removing the beany and bitter flavor from defatted soybean meal with ethanol and isopropyl alcohol were investigated. In the presence of alcohols, soybean protein is extremely sensitive to denaturation when temperature, moisture, and residence time are increased. If protein is to be isolated in good yield and quality, retention of the original, high watersolubility is important, and denaturation must be kept to a minimum. Defatted soybean flakes were successfully debittered by countereurrent washing with aqueous alcohols on a pilot-plant scale, and the entrained solvent was recovered by flash desolventizing without excessive denaturation of protein. Effective debittering was obtained with 95 volume percentage ethanol and 91 volume percentage isopropyl alcohol whereas satisfactory flavor was not obtained with absolute ethanol. The solubility of the nitrogenous compounds in the meal product (Nitrogen Solubility Index—NSI=water-soluble nitrogen×100÷ total nitrogen) was maintained at 68 NSI, or higher, regardless of the solvent system or conditions used when starting with 80 NSI defatted flakes. Residual alcohol in the desolventized products was reduced to 1–2% with the aqueous alcohol system and to less than 1% for the absolute alcohol system. Lower residual values can be obtained by recycling the material through the desolventizing unit. The desolventizing system described is simple, low in cost, and should be useful in any process requiring the rapid removal of solvent from residual solids where heat-sensitive constituents are present.     

Optimized Microemulsion Systems for Detergency of Vegetable Oils at Low Surfactant Concentration and Bath Temperature

Triglycerides and vegetable oils are amongst the most difficult oils to remove from fabrics due to their highly hydrophobic nature; this is all the more challenging as cold water detergency is pursued in the interest of energy efficiency. Recently, extended surfactants have produced very encouraging detergency performance at ambient temperature, especially at low surfactant concentration. However, the salinity requirement for extended surfactants was excessive (4–14%) and there is limited research on extended‐surfactant‐based microemulsions for cold water detergency (below 25 °C). Therefore, extended‐surfactant‐based microemulsions are introduced in this study for cold temperature detergency of vegetable oils with promising salinity and surfactant concentration. The overall goal of this study is to explore the optimized microemulsion formulations with low surfactant and salt concentration using extended surfactant for canola oil detergency at both 25 and 10 °C. It was found that microemulsion systems achieved good performances (higher than those of commercial detergents) corresponding to IFT value 0.1–1 mN/m with the surfactant concentration as low as 10 ppm and 4% NaCl at 25 °C, and as low as 250 ppm and 0.1% (1000 ppm) NaCl at 10 °C. In addition, microemulsion systems were investigated with a different salt (CaCl₂, or water hardness, versus NaCl) at 10 °C, demonstrating that 0.025% CaCl₂ (250 ppm) can produce good detergency; this is in the hardness range of natural water. These results provide qualitative guidance for microemulsion formulations of vegetable oil detergency and for future design of energy‐efficient microemulsion systems.     

Recovery of phytosterols from sunflower oil deodorizer distillates

Phytosterols are usually recovered by crystallization from the deodorizer distillate (DD) of vegetable oils. In this work, the impact of the principal process variables (viz., solvents and cosolvents, cooling rate, crystallization temperature, and ripening time) on the quality and yield of the recovered phytosterols was studied by using a sunflower oil DD “enriched” (i.e., preconcentrated) via transesterification with ethanol (EDD) as a feedstock and commercial hexane as solvent (S), with S/EDD mass ratios of 3 to 5. Water (0 to 4.5 wt%) and ethanol (0 to 10 wt%) were used as cosovents, with crystallization temperatures between 0 and −20°C and crystallization times from 4 to 96 h. The cooling rate was either −20°C/h or “brisk chilling” from 40 to −5°C. The nature and composition of the EDD solvent and cosolvent composite arose as the most important process variable, strongly influencing both the percentage of sterol yield and the purity of the crystals, as well as their filterability and washability. Water-saturated hexane sufficed to give good crystallization, yet the beneficial effect of adding water as the single cosolvent was enhanced by adding small and precise amounts of ethanol. A recovery of sterols as high as 84% (with 36% purity) was achieved by using a single-stage batch crystallization of the S/EDD mixture (S/EDD=mass ratio 4).     

Extraction of lipids from Yarrowia Lipolytica

BACKGROUND: Microorganisms have often been considered for the production of oils and fats as an alternative to agricultural and animal resources. Extraction experiments were performed using a strain of the yeast Yarrowia lipolytica (Y. lipolytica), a high‐lipid‐content yeast. Three different methods were tested: Soxhlet extraction, accelerated solvent extraction (ASE) and supercritical carbon dioxide (SCCO₂) extraction using ethanol as a co‐solvent. Also, high pressure solubility measurements in the systems ‘CO₂ + yeast oil’ and ‘CO₂ + ethanol + yeast oil’ were carried out. RESULTS: The solubility experiments determined that, at the conditions of the supercritical extractor (40 °C and 20 MPa), a maximum concentration of 10 mg of yeast oil per g of solvent can be expected in pure CO₂. 10% w/w of ethanol in the solvent mixture increased this value to almost 15 mg of yeast oil per g of solvent. Different pretreatments were necessary to obtain satisfactory yields in the extraction experiments. The Soxhlet and the ASE method were not able to complete the lipid extraction. The ‘SCCO₂ + ethanol’ extraction curves revealed the influence of the different pretreatments on the extraction mechanism. CONCLUSION: Evaluating the effectiveness of a given pretreatment, ASE reduced the amount of material and solvent used compared with Soxhlet. In all three cases, the best total extraction performance was obtained for the ethanol‐macerated yeast (EtM). Addition of ethanol to the solvent mixture enhanced the oil solubility. Oil can be extracted from Y. lipolytica in two different steps: a non‐selective ethanol extraction followed by TAG‐selective SCCO₂ purification. © 2012 Society of Chemical Industry     

The solubility of SO3 and sulfuric acid in acetone and MEK

Solubility experiments undertaken between 18°C and 24°C showed that solubility of SO₃ in either acetone or methyl ethyl ketone (MEK) is very small. On the other hand, with these solvents sulfuric acid is fully miscible up to a volume ratio of 30:200 acid:solvent.     

Oxidative stability of virgin olive oils

An investigation was carried out on virgin olive oils of the Gentile (Larino), Gentile (Colletorto), Coratina, and Leccino varieties, harvested at different times, to assess their oxidation stability. The olive oils were analyzed by means of peroxide, K_232′ and K₂₇₀ values at 1, 6, 12, and 18 mon of storage in green bottles, in the dark, at temperatures ranging from a mean of 6°C in winter to 12°C in summer. A subsample was also oven-tested at 75°C and then analyzed on a weekly basis using the same oxidative parameters. The less ripe the olives (harvested in the same area during 1 mon), the more resistant the olive oils were to forced oxidation. The amount of total phenols in the oils was found to be directly related, even if to a low degree, to the oleuropein content in the olives and inversely related, to the same degree, to (3,4-dihydroxyphenyl)ethanol. The latter is a derivative of oleuropein; (3,4-dihydroxyphenyl)ethanol content increases as the olives ripen, but it is very low in fresh virgin olive oils, owing to the hydrophilic nature of the phenolic alcohol, which goes mainly into the waste-water during processing. Among the varieties considered, Coratina oils showed the highest resistance to forced oxidation because of their high total phenol content.     

Fatty Acid Profile and Bioactive Compound Extraction in Purple Viper's Bugloss Seed Oil Extracted with Green Solvents

Oil extraction from seeds of purple viper's bugloss (Echium plantagineum) was carried out using different solvents (chloroform:methanol, n-hexane, ethanol, 2-propanol and ethyl acetate) at room temperature and also using Randall extraction. Extraction yields were calculated and oils were analyzed in terms of fatty acid profiles and distribution among lipid classes, total polyphenol content, oxygen radical absorbance capacity (ORAC) and phytosterol content. No considerable differences were found on fatty acid profiles and distribution in oils regardless of the solvent and temperature used for the extraction. However, ethanol combined with Randall extraction (85 °C for 1 hour) offered the best results in terms of total polyphenol content (20.9 mg GAE/100 g oil), ORAC (468.0 μmol TE/100 g oil), and phytosterol amount (437.2 mg identified phytosterols/100 g oil) among all assayed extraction methods. A higher extraction temperature led to significantly higher concentrations of bioactive compounds and ORAC values in the oil when ethanol or 2-propanol were used as extracting solvent, but that was not the case using n-hexane except for the concentrations of β-sitosterol and stigmasterol, which were significantly higher using Randall extraction than room temperature extraction with n-hexane. Ethanol is classified as a “green solvent,” and it could be considered a suitable option to produce oil from E. plantagineum seeds with a higher antioxidant capacity and bioactive compound concentration than the current commercial oil, which is usually extracted with n-hexane.     

Temperature‐dependent solubility of wax compounds in ethanol

The ability of ethanol to dissolve wax compounds, as an alternative to traditional lipid solvents, was investigated for the recovery of cuticular lipids from biomass. The solubilities of fatty esters with carbon chain lengths from 40 to 54 were measured in ethanol over a temperature range of 30–80°C. The greatest increase in solubility was observed between 40° and 60°C for the long chain waxes that are characteristic of flax cuticle lipids. The solubility of a 52‐carbon wax increased by a factor of four over this temperature range. The Van't Hoff equation was used to estimate enthalpy of solution values. Ethanol was an effective lipid solvent at these modestly elevated temperatures and offers an economical method to recover lipid co‐products from biomass prior to conversion to bioethanol.