JPH0124149B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a tocopherol concentrate from a deodorized distillate by-produced in the deodorizing process of fats and oils. α-, β-, γ-, and δ-tocopherols (hereinafter referred to as tocopherols) include soybean oil, rapeseed oil, cottonseed oil, safflower oil, rice bran oil,
Deodorizing scum, deodorizing sludge, Hotwell soapstock, etc. (hereinafter referred to as deodorizing distillate) that are produced as by-products in the deodorizing process of fats and oils such as corn oil and sunflower oil usually contain about 1 to 20% of vitamin E or It is a useful substance as an antioxidant. In addition to tocopherols, the deodorized distillate contains 30 to 60 free fatty acids.
%, sterols and their esters 10-35
%, hydrocarbons 10-30%, glycerides 10-20%,
Other percentages are included. Traditionally, free fatty acids in deodorized distillates are esterified with alcohols to remove steroids.
Tocopherol concentrates have been industrially produced by operations such as adsorption onto inorganic carriers, treatment with ion exchange resins, and molecular distillation. However, the method of performing esterification as a pretreatment not only increases the number of esterification steps but also often leads to loss of tocopherols during esterification. In order to concentrate tocopherols by adsorption onto an inorganic carrier and by the ion exchange resin method, it is necessary to prepare the inorganic carrier and regenerate the ion exchange resin.Furthermore, in the ion exchange resin method, the eluted drug is mixed into the solvent. It is not necessarily an efficient method because it requires removal and requires a large amount of solvent, making the process complicated. Furthermore, the concentration of tocopherols by molecular distillation is limited to a concentration of 40 to 60%, and it is almost impossible to achieve a higher concentration. An object of the present invention is to obtain highly concentrated tocopherols from deodorized distillates and the like using simpler operations than conventional methods with good workability and high yield. The present invention is a method for concentrating tocopherols from a deodorized distillate produced as a by-product in the deodorizing process of vegetable oils and fats, in which the deodorized distillate is subjected to distillation, free fatty acids in the deodorized distillate are removed, and then hydrogenation is performed. do the
The present invention relates to a method for producing a tocopherol concentrate, which is characterized by further performing solvent fractionation to extract tocopherols. As mentioned above, the deodorizing distillate used in the present invention is deodorizing scum, deodorizing sludge, hotwell soapstock, etc., which are produced as by-products in the oil and fat deodorizing process. Alternatively, a tocopherol-containing material that has been concentrated by distillation such as reduced-pressure steam distillation, fractionation such as solvent fractionation, or adsorption using silica gel can also be used as a starting material. The distillation for removing fatty acids from the deodorized distillate is preferably vacuum steam distillation or molecular distillation. For example, vacuum steam distillation is carried out at a temperature of 170 to 230°C, preferably 190°C.
It is carried out at ~210°C and a pressure of 25 mmHg or less, preferably 15 mmHg or less. Also, molecular distillation can be carried out at a temperature of 150°C, for example.
It is carried out at ~250°C, preferably 180~240°C, and a pressure of 0.01 Torr or less, preferably 0.003 Torr or less. During distillation,
Although some tocopherols are also distilled out, it is possible to suppress the distillation of tocopherols by adjusting the distillation temperature and degree of pressure reduction within the above ranges. Also,
The lower the acid value at the end point of distillation, the better.
Usually it is 5 or less. By performing distillation under such conditions, fatty acids in the deodorized distillate can be removed. After removing fatty acids, hydrogenation is performed, but before that, tocopherols may be concentrated if necessary. As this concentration treatment, the above-mentioned distillation, fractionation, and adsorption operations performed on the deodorized distillate can be employed. Next, the step of hydrogenating the deodorized distillate from which fatty acids have been removed is carried out by heating under pressure in a hydrogen atmosphere in the presence of a metal catalyst. Metals used as hydrogenation catalysts include palladium, platinum,
Examples include rhodium, ruthenium, and nickel, and are usually supported on a support such as metal, carbon black, silica, or ion exchange resin. Hydrogenation is carried out according to the conventional method at a temperature of 150 to 250℃.
It is carried out under a hydrogen pressure of 25 kg/cm ² and the end point of hydrogenation is aimed at an iodine value of 50 or less. Hydrocarbons, triglycerides, etc. with unsaturated bonds present in the deodorized distillate in the hydrogenation process undergo hydrogenation to increase their melting points, and their solubility decreases during solvent fractionation in the next process. The components remain as solvent-insoluble components during solvent fractionation, and tocopherols are effectively extracted into the solvent layer. The hydrogenated product is then subjected to solvent fractionation. Solvents used here include alcohols or hydrous alcohols such as methanol, ethanol, propanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dimethyl ether, diethyl ether, and dipropyl ether; methyl acetate; Examples include one or a mixture of two or more of esters such as ethyl acetate and hydrocarbons such as hexane, heptane, petroleum ether, and benzene. The amount of solvent used is 2 to 50 times (by volume) the amount of deodorized distillate, fatty acid removed product, and hydrogenated product.
degree is desirable. The temperature during fractionation may be below the boiling point of the solvent used. Although the temperature is preferably 20°C or lower, it is not necessarily necessary to lower the temperature to 0°C or lower. A solvent is added, mixed, allowed to stand, and a supernatant (solution layer) is separated, from which the solvent is removed to obtain a tocopherol concentrate. The solvent extraction residue mainly contains hydrogenated hydrocarbons, triglycerides, etc. in the deodorized distillate. The present invention has better workability in the step of concentrating tocopherols from a deodorized distillate than conventional methods, is simple to operate, and can obtain a tocopherol concentrate with high yield. Examples are shown below. Example 1 Soybean oil deodorized distillate [tocopherol content 17.3
% (according to Emily Engle method, same below) Acid value
71.0, iodine value 75] was weighed into a Claisen flask and subjected to vacuum steam distillation at 200°C and 7 mmHg, and the distillation was completed when the acid value reached 3.7.
Solvent removal was performed to obtain 631 g of deodorized soybean oil distillate from which fatty acids had been removed. Nickel hydrogenation catalyst (nickel content 25% dispersed in hydrogenated oil) 0.5% (3 g) to 600 g of the fatty acid removed product
was added and heated at 200° C. for 2 hours under a hydrogen pressure of 2.5 Kg/cm ² to obtain a hydrogenated product (iodine value 21). After separating the catalyst, divide it into 100g each, add 300g of ethanol or hydrous ethanol shown in Table 1,
The mixture was stirred at 45°C for 10 minutes, cooled to 20°C, stood still, and the ethanol layer was separated. The solvent was removed to obtain a tocopherol concentrate (Table 1). From the results in Table 1, it can be seen that tocopherols were concentrated with good yield.

[Table] Example 2 Cottonseed oil deodorized distillate (tocopherol content 10.4
%, acid value 76.0, iodine value 98) was weighed into a Claisen flask and subjected to vacuum steam distillation at 195-198°C and 14 mmHg. Distillation was terminated when the acid value reached 17, hydrogenation was performed in the same manner as in Example 1, and extraction was performed with methanol or aqueous methanol (5 times the amount). The results are shown in Table-2. From the results in Table 2, it can be seen that tocopherols were concentrated with good yield.

[Table] Example 3 Soybean oil deodorized distillate (tocopherol content 16.8
%, acid value 70.5, iodine value 76) 25Kg at 200-205℃,
Vacuum steam distillation was performed at 15 mmHg. Acid value is 2.0
Distillation was terminated at the point at which 15.8 kg of fatty acid-free deodorized distillate of soybean oil was obtained. 15Kg of the fatty acid removed product is heated to 180~ using a molecular distillation device.
Distillation was carried out at 240℃ and 0.002Torr. 5.3 kg of molecular distillation fraction was obtained. The tocopherol content of the fraction was 62.7%. After 5.0 kg of the fraction was hydrogenated in the same manner as in Example 1, it was separated into 1 kg portions, 10 kg of ethanol or water-containing ethanol in Table 3 was added to each portion, and tocopherols were extracted at 25°C to obtain a tocopherol concentrate. (Table 3). From the results in Table 3, it can be seen that tocopherols were concentrated with good yield.

[Table] Example 4 Safflower deodorized distillate (tocopherol content
Weigh 1000g of 5.5%, acid value 78.2, iodine value 89) into a Claisen flask, 200-205℃ 6-8mm
Vacuum distillation was performed with Hg. Distillation was terminated when the acid value reached 0.6, and the iodine value reached 10 as in Example 1.
After hydrogenation until
Extraction was performed using The results are shown in Table 4. From the results in Table 4, it can be seen that tocopherols were concentrated with good yield.

[Table] Example 5 Soybean oil deodorized distillate (tocopherol content 11.3
%, acid value 72.0, iodine value 78) 20Kg at 200-220℃,
Molecular distillation was performed at 0.01 Torr. 1.5 kg of the obtained fraction (tocopherol content 33.5%, acid value 5.1) was hydrogenated in the same manner as in Example 1, and then divided into 250 g portions, and 2.5 kg of ethanol or hydrous ethanol shown in Table 5 was added. Tocopherols were extracted at 20°C to obtain a tocopherol concentrate.

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Claims (1)

[Claims] 1. A method for concentrating tocopherols from a deodorized distillate produced as a by-product in the deodorizing process of fats and oils, in which the deodorized distillate is subjected to distillation to remove free fatty acids in the deodorized distillate, and then 1. A method for producing a tocopherol concentrate, which comprises performing hydrogenation and further solvent fractionation to extract tocopherols. 2. The method according to claim 1, wherein the fatty acid-removed product of the deodorized distillate is subjected to concentration treatment before hydrogenation. 3. The method according to claim 1, wherein the solvent for solvent fractionation is selected from methanol, ethanol, and hydrated products thereof. 4 The solvent for solvent separation is acetone, ethyl acetate,
A method according to claim 1, wherein the method is selected from hexane and petroleum ether.