JPS59118095A - Preparation of monoglyceride - Google Patents

Abstract

PURPOSE:To prepare a high-quality monoglyceride free from the exposure to high temperature and useful as an additive for foods, pharmaceuticals, etc., by alcohol-group exchange reaction of a fatty acid ester with glycerol in the presence of a fat hydrolase adding an adsorbent, etc. to the reaction system. CONSTITUTION:The objective monoglyceride is prepared by adding (A) <=10wt% of an adsorbent (e.g. active charcoal) or <=5wt% of a calcium salt (based on the component B) to (B) a reaction system composed of (i) a fatty acid ester and (ii) glycerol, and treating the mixture with (C) a catalyst comprising a fat hydrolase to effect the alcohol-group exchange reaction of the component (i) and (ii). USE:Additive for cosmetics, feeds, synthetic resins, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing monoglyceride from fatty acid ester and glycerin using an oil-fat hydrolase.

Monoglycerides are esters with hydroxyl groups that have surface-active properties and are widely used in foods, cosmetics, pharmaceuticals, feeds, synthetic resins, etc.

Among the manufacturing methods of monoglycerides, chemical methods include:
Various catalysts have been used to partially hydrolyze fats and oils (triglycerides), esterify fatty acids and glycerin, and transesterify fats and oils with glycerin. Enzyme reaction methods using fat hydrolase as a catalyst include partial hydrolysis of fats and oils (Japanese Patent Publication No. 48-17525, etc.), fatty acid and glycerin esterification method (Japanese Patent Publication No. 775 Sho 51, etc.).
No. 4, Special Publication No. 57-23535). Reactions using these fat and oil hydrolases have drawbacks such as the inability to use fats and oils or fatty acids with high melting points because there are almost no enzymes that are thermally stable for long periods of time. Furthermore, the monoglyceride content in the reaction products obtained by these enzymatic reactions is low and cannot be used as monoglycerides as they are, so it is necessary to increase the purity by post-treatment such as molecular distillation. Therefore, it is strongly desired to increase the monoglyceride content in the reaction product.

The present inventors have conducted intensive studies to eliminate these drawbacks and to not only make it possible to produce monoglycerides of various fatty acids in a low-temperature reaction that does not deactivate the oil-fat hydrolase, but also to increase the yield of monoglycerides. discovered that monoglycerides were produced in high yields when adsorbents and calcium salts were added alone or in combination when the entire reaction system was liquefied using a fatty acid ester and an oil-fat hydrolase was allowed to act, and the present invention was realized. It was completed.

That is, the present invention is a method for producing monoglycerides in which an adsorbent or a calcium salt is added to a reaction system consisting of a fatty acid ester and glycerin, and an alcohol group exchange reaction is carried out using a fat hydrolase as a catalyst.

The fatty acid ester used in the present invention has 4 or more carbon atoms.
Fatty acids with a chain length of 22 and methyl alcohol, ethyl alcohol, propyl alcohol, butylfurfur,
It is an ester with alcohols such as ethylene glycol, propylene glycol, and glycerin. These fatty acid esters can be used alone or in combination of two or more.

As the glycerin used in the present invention, commercially available glycerin can be used. However, care must be taken not to increase the amount of water in the reaction system too much.

The adsorbent used in the present invention preferably has a large specific surface area, and includes, for example, activated carbon, activated clay, acid clay, and silica gel. The amount added is preferably 10% by weight or less based on the mixture of fatty acid ester and glycerin. In addition, calcium salts include calcium chloride,
Calcium phosphate, calcium hydrogen phosphate, calcium carbonate, etc. can be used, and the amount added is preferably 5% by weight or less based on the mixture of fatty acid ester and glycerin. Adsorbents and calcium salts that are water-insoluble are added as powders, while water-bathable ones are added after being dissolved in water.In the present invention, the water content in the reaction system is 10
It is desirable not to exceed % by weight.

The fat and oil hydrolase used as a catalyst in the present invention is
For hydrolysis ability, any type of enzyme can be used, such as an enzyme originating from Candida cylindracea that cleaves glycerides at the 1, 2 and 3 positions, an enzyme originating from Rhizopus niveus that cleaves only the 1 and 3 positions, or an enzyme obtained from watermelon organ. However, preferably it is an oil/fat hydrolase that only cleaves at the 1.3 position.

The alcohol-equal exchange reaction according to the present invention is carried out by thoroughly mixing the fatty acid ester, glycerin, adsorbent, or calcium salt, or a mixture thereof, and adding a fat-and-oil hydrolase at a temperature range that does not inactivate the enzyme. conduct. The reaction temperature is a temperature that does not deactivate the enzyme, preferably 30-45
It is C. The reaction is carried out while maintaining the specified temperature and stirring.
Do this for ~5 days. After the reaction is completed, heat is applied to separate the oil layer and the glycerin layer, and the oil layer is collected. In order to remove the e-adhesive remaining in the oil layer, the obtained oil layer is subjected to purification treatments such as filtration and centrifugation.

The effect of adsorbents and calcium salts on this reaction is
It is thought that the reaction is promoted by adsorbing fatty acid ester, glycerin, and fat hydrolase to increase the surface area and improve the contact efficiency, or by increasing the stability of the fat hydrolase.

Since the method for producing monoglycerides according to the present invention uses fatty acid esters, high melting point fatty acids can also be used as low melting point esters. Not only can it be used to produce monoglycerides by low-temperature enzymatic reactions, but monoglycerides can be obtained in high yields of 50 to 70% by weight. In addition, the monoglyceride obtained is of excellent quality because it has not undergone a high temperature history.
In particular, the quality of the monoglyceride obtained when the reaction is performed with the addition of an adsorbent is even better, resulting in a product that is ideal for use in fields such as cosmetics and pharmaceuticals.

Next, the present invention will be explained by examples. In addition, below...
The total monoglyceride content was determined by equilibrating the sample with perchloric acid to make the ratio of 1- and 2-monoglycerides constant, and then measuring 1-monoglyceride by the periodic acid method.
The total monoglyceride content was calculated by multiplying the obtained value by a constant coefficient (Tsu 1), Shigeru, "Monoglyceride", 1960, Maki Shoten; p. 53).

Example l Triolein 45P and glycerin (moisture capacity 7wt@%)
To a mixture of 100 J' of oil and fat hydrolase 15/derived from Rhizopus delmar and an adsorbent were added, and an alcohol group exchange reaction was carried out for 48 hours with stirring at 30C. After the reaction was completed, the glycerin layer was separated and the adsorbent was separated. The total monoglyceride content in the obtained oil layer components was as shown in Table 1 together with the amount of adsorbent added.

The results in Table 1 show that the total monoglyceride content increases with the addition of adsorbent.

Table 1 Total monoglyceride content (weight f & 4) Note) Added amount is weight f% based on the total amount of fatty acid ester and glycerin Example 2 Methyl stearate 507' and glycerin (moisture content 1
0% by weight) 1007' was added with 1.51 of an oil-fat hydrolase originating from the chromophore Ctellium and a calcium salt, and an alcohol group exchange reaction was carried out at 45C for 72 hours. After the reaction was completed, the glycerin layer was removed to obtain an oil layer. The total monoglyceride content in the oil layer components was as shown in Table 2 depending on the type and amount of calcium salt.

The results in Table 2 show that the total monoglyceride content increases with the addition of calcium salts.

Table 2 Total monoglyceride content (wt%) Note) The amount added is the same as the note in Table 1. Example 3 Methyl palmitate 35#l, )su/4 Lumitin 151
1. Hydrolase derived from Supergillus 2. OP, activated carbon 3t and calcium carbonate 2! was added and a alcohol exchange reaction was carried out at 40C for 72 hours.

After the reaction was completed, the same treatment as in Example flj 1 was carried out, and the total monoglyceride content of the oil layer was determined to be 57.

The total monoglyceride content was 35 if the reaction was carried out in exactly the same way except for the addition of adsorbent and calcium salt.
%Met.

An increase in the total monoglycerides B i is observed with the addition of adsorbents and calcium salts.

Patent applicant: NOF Corporation

Claims (1)

[Claims] 1. A method for producing monoglycerides, which comprises adding an adsorbent or a calcium salt when producing monoglycerides by an alcohol group exchange reaction between a fatty acid ester and glycerin in the presence of an oil-fat hydrolase.