JPS5850238B2 - How to collect sterol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to deodorized distillate (hereinafter abbreviated as deodorized distillate) produced as a by-product from a vacuum steam deodorizing tower during the refining and processing of animal and vegetable oils and mixed oils thereof.

) or the distillation residue by-produced from the fatty acid distillation column (hereinafter abbreviated as fatty acid distillation residue).

) is used as a starting material to produce a highly purified sterol (hereinafter in the present invention, free sterol will be simply referred to as sterol).

) in a high yield and economically.

The composition of the deodorized distillate or fatty acid distillation residue of the starting material is sterols (in the present invention, unless otherwise specified, free sterols and sterol derivatives are collectively referred to as sterols).

) It is a multi-component mixture containing tocopherol, hydrocarbons, various aliphatic compounds such as diglycerides, monoglycerides, triglycerides, fatty acids, carotenoids, terpenes, aldehydes, ketones, and unknown components.

Among the above ingredients, sterols in particular have a wide range of uses as pharmaceutical raw materials, cosmetic bases, feed additives, etc. Sterols can also be used as a pretreatment for separating and purifying tocopherols from the raw materials of the present invention. Collecting is an essential process.

Conventionally, there have been many studies on methods for separating and purifying sterols from deodorized distillates and fatty acid distillation residues.

These separation and purification methods can be broadly divided into three methods: (a) solvent fractional crystallization method, (b) urea adduct method, and ←→ metal chloride adduct method.

(In method (4), aqueous ethanol is added as a solvent to increase the yield, but the purity and yield are both low, and 70%
It is about 80%.

Methods (b) and ()) can obtain products with a high purity of about 80 to 90%, but the operations are complicated and a large amount of organic solvent is used, so it is not necessarily an economical separation method as an industrial treatment method. , it can hardly be called a purification method.

In view of the above-mentioned drawbacks of the conventional methods, the present inventor conducted intensive research with the aim of efficiently collecting sterols from deodorized distillates or fatty acid distillation residues with simple collection operations and high yield and purity. The so-called hydrophilization method was used to separate components with different melting points from mixtures and fatty acid ester mixtures (Japanese Patent Publication No. 51-2087, or Japanese Patent Publication No. 51-2483).
) used as part of the process of the present invention, i.e. a deodorized distillate or fatty acid distillation residue which is a multi-component mixture as described above with a composition completely different from the fatty acid mixture or fatty acid ester mixture. By applying this hydrophilization method to a part of the process of collecting only sterols from them, the purpose of the present invention can be achieved without using any organic solvent or using only a small amount of organic solvent. As a result of this success, the present invention provides a method for obtaining deodorized distillates or fatty acid distillation residues, which are the starting materials, either directly or after first saponification, acid decomposition, or transesterification with lower alcohols. The resulting product is heated to a temperature above the melting point to melt it, then an aqueous wetting agent solution is added, mixed to uniformly emulsify, and then cooled to remove the components contained in the deodorized distillate or fatty acid distillation residue. The sterols contained in the sterols are suspended in an aqueous wetting agent solution and separated from the oil layer, and the sterols are collected by heating the final suspension, or the suspension is mixed with water. The present invention provides a method of extracting sterols with an organic solvent with low solubility, preferably a C4 to C1o aliphatic lower alcohol, and collecting the sterols as crystals by cooling the extract.

To explain in more detail, in order to effectively utilize the principle of the above-mentioned hydrophilization method in the present invention, the purpose of collecting the sterol of the present invention cannot be achieved by simply applying the method used for conventional oil and fat mixtures. It is difficult to achieve this, and in the case of the present invention, it is necessary to set conditions unique to the present invention that are suitable for the starting material, and for this purpose, it is necessary to carry out appropriate pretreatment.

In order to more effectively obtain highly purified sterols, it is necessary to introduce a new method for subsequent processing.

In other words, the present invention makes it possible to effectively collect sterols with high purity from the raw material of the present invention, which cannot be achieved by simply applying known hydrophilization methods, by adding new operations to the steps before and after applying the hydrophilization method. This is a novel method that is completely different from any of the conventional methods for separating and purifying sterols.

Although it is possible to collect sterols from the starting material without processing the deodorized distillate or fatty acid distillation residue of the raw material of the present invention, the composition of the deodorized distillate or fatty acid distillation residue that is the starting material Usually, it varies significantly depending on the type, variety, refining, and processing conditions of the animal and vegetable oils and fats and mixtures thereof used as raw materials, and its composition includes substances with surfactant effects such as monoglycerides and diglycerides. As mentioned above, it is included.

Changes in the abundance of substances with such surfactant effects have an extremely important effect on the amount and concentration of the wetting agent aqueous solution used when applying the hydrophilization method, so sterols can be produced with high purity and high yield under stable conditions. It becomes difficult to collect at a certain rate.

Therefore, if there is a large amount of a substance having a surfactant effect, in order to reduce this effect, in the present invention, the deodorized distillate or fatty acid distillation residue is first treated by saponification, acid decomposition, or aliphatic lower alcohol. Through pretreatment such as transesterification with esters, various glycerides are eliminated and, at the same time, most of the sterols are converted to sterols.

As a result, the composition of the starting material was simplified, the conditions for sterol collection were stabilized, and sterols could be obtained in high yield and purity.

In the operation of the present invention, an aqueous wetting agent solution at the same temperature as the starting material is added to the starting material to form an emulsion. , alcohol sulfate esters, sulfated fatty acid monoglycerides, soaps, etc.

The concentration of the wetting agent aqueous solution varies depending on the composition of the starting material, but is generally within the range of 0.1 to 5.0%, and the amount of the wetting agent aqueous solution used is 1 to 10 times the weight of the starting material, and at the same time Add electrolyte to the aqueous wetting agent solution.

As the electrolyte, for example, an alkali metal or alkaline earth metal chloride or sulfate is used, and the concentration is 0.1 to 10%.
It is preferable to adjust the solution so that it becomes an aqueous solution.

Next, the resulting emulsion is cooled while being mechanically stirred using a stirrer or the like, thereby dispersing the crystallized sterol into the aqueous wetting agent solution.

This is separated, for example, by a centrifuge into a suspension of sterols dispersed in an aqueous wetting agent solution and a liquid oil layer that has not migrated into the aqueous wetting agent solution.

In order to collect sterols from the suspension obtained here, the suspension is heated to 170 to 220°C.

More preferably, the suspension is preheated to 80°C to 140°C, impurities other than sterols are melted in advance, and a liquid layer is separated from the sterol suspension, and then the suspension is heated to 170°C.
It is preferable to collect sterols by heating to ~220°C.

Furthermore, it is possible to extract and separate sterols from the suspension using an organic solvent.

By adding and stirring a chlorine-based, ether-based, or aliphatic alcohol-based solvent such as a ketone, chloroform, or carbon tetrachloride, which has low compatibility with water, especially a C4 to CIO aliphatic lower alcohol, to the suspension. , sterols can be collected by transferring them into a solvent and removing the solvent.

At this time, by cooling the solvent micella and crystallizing the sterol, even higher purity sterol crystals can be obtained.

The advantages of the present invention are that it compensates for the disadvantage of using a large amount of organic solvent, which was uneconomical as an industrial treatment method, based on the principle of fractional crystallization seen in the conventional method, and that it can produce sterols of high purity and high yield. This made it possible to collect sterols, and it will greatly contribute to the industrial production of sterols in the future.

Example 1 Fatty acid distillation residue 500P (sterol content 21.5%)
Add the aqueous wetting agent solution No. 11 (containing 0.5% sodium lauryl sulfate, 1% N02SO4) to the solution, and start cooling from 60°C with stirring at a cooling rate of 5°C/hour.

The mixture was then separated into a sterol suspension layer and a liquid oil layer.

heating the suspension layer to 170°C to melt the sterol;
separated.

107.5P of sterol crystals (yield: 85.0%) were obtained.

The purity of the sterol measured by gas clostography was 85.0%.

Example 2 1 kg of deodorized distillate (sterol content 22.0%)
0% KOH aqueous solution 0.51! A solution dissolved in ethyl alcohol 31 was added for saponification, neutralized with a 10% aqueous H2SO4 solution, and washed with water to obtain a saponified deodorized distillate.

11 for 500y of saponified deodorized distillate! Add a wetting agent aqueous solution (containing 0.5% sodium oleate, 1% N02SO4), stir, cool, and centrifuge according to Example 1, and add n-butanol to the resulting suspension layer for extraction. By cooling the extraction solution, sterol crystals 102
．． 5f (yield 88.1%) was obtained.

The sterol purity measured in the same manner as in Example 1 was 94.
It was 5%.

Example 3 2 kg of deodorized distillate (sterol content 26.8%)
5 kg of H2SO4-methanol (volume %) was added to carry out a transesterification reaction, and the mixture was washed with water to obtain a transesterified deodorized distillate.

1.51 aqueous wetting agent solution (0.5% lauryl sulfate ester soda, 1
%N02SO4) and stirred according to Example 1,
After cooling and centrifugation, the resulting suspension was heated to 80°C to melt the high melting point part and separate as a liquid layer, and the suspension was further heated to 170°C to melt and separate the sterols. .

Sterol crystals, 128fI (yield 86.2%) were obtained.

Sterol purity measured in the same manner as Example 1 was 89.0%
Met.

Claims (1)

[Claims] 1. When refining and processing animal and vegetable oils and their mixed oils, the deodorizing distillate by-produced from the vacuum steam deodorizing tower or the distillation residue by-producing from the fatty acid distillation tower (hereinafter referred to as starting materials) may be used as is or by saponification, acidification, etc. After decomposition or transesterification with an aliphatic lower alcohol, the resulting product is heated to a temperature above the melting point to melt it, and then o, i to 10% by weight (hereinafter all percentages are by weight). %) concentration of an electrolyte in an amount of 1 to 10 times the weight of the starting material, mix to uniformly emulsify, and cool the starting material. The sterols contained in the raw materials are suspended and precipitated in an aqueous wetting agent solution, separated from the oil layer, and the final suspension is preheated to 80 to 140°C or without preheating. After preliminarily melting impurities other than sterols by heating to 170-220°C and separating them from the sterol suspension as a liquid layer, the suspension was heated to 170-220°C.
The sterols are extracted by heating to 20°C to collect the sterols, or by adding an organic solvent with low compatibility with water to the suspension, and the sterols are collected as crystals by cooling the extract. A method for collecting sterols from deodorized distillate or fatty acid distillation residue.