JPS6229550A - Selective separation of polyfunctional unsaturated fatty acid ester and saturated fatty acid ester - Google Patents

Abstract

PURPOSE:To selectively and efficiently extract a polyfunctional unsaturated fatty acid ester, by extracting and separating the above-mentioned unsaturated fatty acid ester and a saturated fatty acid ester with a specific fluid in the presence of ethyl acetate under specific conditions. CONSTITUTION:A polyfunctional unsaturated fatty acid, saturated fatty acid ester and a mixture thereof are brought into contact with a fluid, chemically inert to the above-mentioned esters and having within 0-50 deg.C critical temperature range, e.g. ethane, ethylene or gaseous carbon dioxide, under conditions of the critical temperature or above under critical pressure or above, preferably a temperature 1-50 deg.C higher than the critical temperature of the above- mentioned fluid under a pressure 100-250kg/cm<2> higher than the above- mentioned critical pressure thereof to efficiently and selectively transfer the above-mentioned unsaturated fatty acid ester into the above-mentioned fluid. Thereby, the polyfunctional unsaturated fatty acid ester and the saturated fatty acid ester are advantageously extracted and separated without causing denaturation nor deterioration.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyunsaturated fatty acid esters and saturated fatty acid esters, which are contained in many plants such as seafood and vegetables, for example, in the range of 0 to 50°C. A fluid in
Above its critical temperature and critical tool 1-. When the polyunsaturated fatty acid esters and the saturated fatty acid esters are brought into contact and extracted and separated under This invention relates to a method for selectively separating polyunsaturated fatty acid esters and saturated fatty acid esters from which fatty acid esters can be extracted.

More specifically, the present invention provides that when polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof are extracted and separated using the fluid, the extraction treatment is carried out in the presence of addition of ethyl acetate. This paper relates to a method for selectively separating polyunsaturated fatty acid esters and saturated fatty acid esters.

When extracting and separating polyunsaturated fatty acid esters, saturated fatty acid Nisdels, and mixtures thereof using the fluid, the polyunsaturated fatty acid esters and saturated fatty acid esters have extremely high molecular weight. Because of their low volatility, it is difficult to extract and separate polyunsaturated fatty acid esters with high selectivity and high yield. Unreleased +51 is
From such polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof, polyunsaturated fatty acid esters can be efficiently and easily manipulated without causing any disadvantageous modification or alteration. This invention relates to a selective separation method for polyunsaturated fatty acid esters that can be extracted and separated.

In recent years, with the deterioration of the energy situation, emphasis has been placed on recording energy consumption and diversifying energy sources, and energy saving processes have been emphasized. Improvements in efficiency, higher selectivity, milder reaction conditions, etc. can be considered.

Conventional common separation and extraction techniques for fatty acid esters include the "one-shot fractionation method, surfactant-applied fractionation method, molecular distillation method, solvent fractionation method, and extraction method using furfural and propane." It is difficult to concentrate and separate polyunsaturated fatty acid esters from low melting point, high iodine value oils by these methods stably, quickly, inexpensively, and to a fraction.For example, 1) natural fractionation method is Although it has the advantage of being low cost, it takes a long time to crystallize and the classification efficiency of polyunsaturated fatty acid esters is not high. , the process is complicated as it requires a descaling device to remove easily volatile substances in advance.The solvent fractionation method has a somewhat high yield and yields polyunsaturated fatty acid esters, but it requires quite low temperatures. This increases the cost and makes it difficult to dissolve and remove.

The present invention is capable of extracting and separating unsaturated fatty acid esters from polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof. The purpose of the present invention is to provide a method for separating the right and left under certain conditions.

The present invention provides polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof, which have a critical temperature of 0 to 50°C.
When contacting a fluid in the range of -E and above its critical temperature and above the critical pressure, it is carried out in the presence of ethyl acetate to produce polyunsaturated fatty acid esters in a high yield, selectively and easily. It is characterized by extraction and separation.

The present invention will be explained in detail below.

Generally, when a gas and a solid or liquid are brought into contact, the amount of the solid or liquid that changes to the gas phase under normal pressure and room temperature is extremely small. However, when the type of gas is appropriately selected and the gas is at a temperature or pressure higher than the critical temperature, the amount of solid or liquid transferred to the gas phase increases dramatically. However, polymer compounds with large molecular weights and low vapor pressures have difficulty transferring into carbon dioxide gas even if they are brought into contact with carbon dioxide gas at a pressure higher than the critical pressure. [Chem, -1 ng.

-Tech, 55 (11), 890 (1983)
; C, Hubert and K.

Ern5t] The present inventor has developed chemically inert, below-critical temperature and critical dose OLs, polyunsaturated fatty acid esters, saturated fatty acid esters and mixtures thereof. The present invention was achieved based on the discovery that polyunsaturated fatty acid esters can be extracted and separated advantageously when brought into contact with a fluid in the following state under appropriate conditions.

Therefore, the contact conditions between the extraction treatment system and the fluid in the present invention are as follows. Generally, the higher the pressure, the greater the solubility, so it is desirable to have the pressure as high as possible, but considering economic efficiency, the pressure should be 150 to 500 kg/cm7.
is the 91 most desirable range. Although the temperature must be above the critical temperature, a temperature range of 1 to 50°C higher than the critical temperature is used.

The fluid used in the present invention contains 1 to 20% by weight of ethyl acetate.
It is a fluid whose critical temperature is around room temperature. A fluid with a critical temperature of 0-50°C was chosen. Table 1 below shows the critical temperatures of gases used in the present invention.

Fluid use star: Extract ♀, required polyunsaturated fatty acid ester: 11. Depending on the situation, use 200 to 450 times the amount of raw fatty acid ester I.

Unlike the conventional method, according to the method No. 2, polyunsaturated fatty acid esters can be extracted and separated at approximately room temperature and at low cost using a clock wheel operation. The fatty acid ester composition was determined by gas chromatography after conversion to fatty acid methyl ester. Examples are illustrated below, but the present invention is not limited to these examples.

Example-1 10.31g of triolein was placed in an extractor and heated to 40°C.
7Rm gas containing 4% ethyl acetate was blown into this at a rate of 60L/h at 200Kg/Cm2 to bring it into contact. Here, the above fluid in which triolein is dissolved is
After passing through a filter and a pressure regulating valve, the triolein is introduced into a molecular atomizer at normal pressure and a temperature of 0°C.
Ethyl acetate was removed under reduced pressure to obtain triolein. The triolein extraction rate was as shown in Table 2. It can be seen that the method of the present invention significantly increased the yield of unsaturated components. (The same applies to the effects of the following examples.) Example-2 Triolein 9.71g, tristearin 9°73g
After charging it into an extractor, it was treated in the same manner as in Example-1 to obtain an extract. The fatty acid composition of this extract is shown in Table 3 (C1
0:1/C18:O=8, as shown in 3).

Example-3 9.60 g of methyl stearate and 9.60 g of methyl merate.
71 g was placed in an extractor and treated in the same manner as in Example-1 to obtain an extract. The molar ratio of the fatty acid composition of this extract (CI8:
2/C18:0=6, 2) as shown in Table 3.

Example-4 9.82 g of methyl stearate and methyl olein were placed in an extractor, kept at 40°C, and ethyl acetate was added to the extractor.
Heavy? -% containing i3M gas at 280Kg/cm2.6
The mixture was blown at a rate of 0 L/h and treated in the same manner as in Example 1 to obtain an extract. The molar ratio of fatty oxygen composition of this extract was as shown in Table 3.

Table 1 Table 2 Table 3

Claims (1)

[Claims] 1. Polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof, with a fluid that is chemically inert to them and whose critical temperature is in the range of 0 to 50°C; The unsaturated fatty acid ester is selectively transferred into the fluid with substantially high efficiency by contacting under conditions of a critical temperature or higher and a critical pressure in the presence of added ethyl acetate. This is a selective separation method for polyunsaturated fatty acid esters and saturated fatty acid esters. 2. Claim (1) in which the contact between polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof with a fluid is carried out at a temperature 1 to 50°C higher than the critical temperature of the fluid. Method described. 3. Contact the fluid with polyunsaturated fatty acid esters, saturated fatty acid esters, and mixtures thereof at a pressure of 100 Kg/cm^2 to 250 Kg/cm^2 below the critical pressure of the fluid.
The method according to claim (1), which is carried out under high pressure conditions. 4. The method according to claim (1), (2) or (3), wherein the fluid is ethane, ethylene or carbon dioxide. 5, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] ROCOR' [2] Polyunsaturated fatty acid esters and unsaturated fatty acid esters (R
is unsaturation degree 0-5, carbon number 16-20; R' is CH_3
or claim No. (1) expressed as C_2H_5.
) method described in section.