JPH07115983A - Method for producing sugar or sugar alcohol fatty acid ester by enzymatic method - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a method capable of producing an ester with high productivity when reacting a sugar or a sugar alcohol with a fatty acid using an enzyme as a catalyst without precisely controlling the reaction conditions. [Structure] When a sugar or sugar alcohol and a fatty acid are reacted in the presence of an enzyme such as lipase to produce an ester, the reaction is carried out without solvent and under reduced pressure while intermittently adding water to the reaction system.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a fatty acid ester of sugar or sugar alcohol. In particular, the present invention relates to a method for producing a fatty acid ester of sugar or sugar alcohol suitable as a food additive by carrying out a reaction under a mild condition without a solvent by the catalytic action of an enzyme.

[0002]

2. Description of the Related Art As a method for producing a fatty acid ester of sugar or sugar alcohol, a chemical synthesis method in which a sugar or sugar alcohol and a fatty acid or a lower alcohol ester thereof are reacted in the presence of an acid or an alkali is used. However, in this method, since the reaction is performed at a high temperature of 100 to 250 ° C., there is a problem that by-products are easily generated and the product is easily colored. As a manufacturing method without such problems,
A method using an enzyme capable of hydrolyzing fats and oils such as lipase has been studied (JP-A-61-268192, 62-1).
58992, 62-195292, 63-14948). Although it is considered that water is necessary for the reaction to proceed in this method, the presence of a large amount of water hinders the reaction. As a method for solving this problem, it has been proposed to start the reaction in the presence of a large amount of water, reduce the atmosphere during the reaction, and allow the reaction to proceed while removing water. However, the relationship between the amount of water present and the progress of the reaction has not been fully clarified yet.

Although a method of carrying out the reaction in the presence of an organic solvent has also been proposed, the organic solvent often reduces the activity of the enzyme, and the product ester is often used as a food additive. Therefore, it is desirable to avoid the use of organic solvents.

[0004]

As described above, there have been reported a number of methods of reacting sugars or sugar alcohols with fatty acids using an enzyme as a catalyst, but none has been found to be satisfactory. Therefore, the present invention provides a method for producing a fatty acid ester of sugar or sugar alcohol by an enzymatic method which is excellent in operability as an industrial process.

[0005]

Means for Solving the Problems The present inventors have found that when an aqueous solution of sugar or sugar alcohol and a fatty acid are reacted with an enzyme as a catalyst without solvent and under reduced pressure while removing water, a reaction rate is obtained at a certain point. However, it was found that the reaction rate was recovered by adding water, and the present invention was completed.

The present invention will be described more specifically as follows.
Sucrose is usually used as the sugar used as one of the raw materials in the present invention. But xylose, glucose,
It is also possible to use monosaccharides such as fructose and disaccharides other than sucrose such as maltose, trehalose and lactose. If desired, a trisaccharide such as maltotriose can also be used. As the sugar alcohol, it is preferable to use one having 4 to 12 carbon atoms such as erythritol, xylitol, sorbitol and maltitol.

As the fatty acid which is the other raw material, a saturated or unsaturated fatty acid having 6 to 22 carbon atoms is usually used. For example, caproic acid, capric acid, caprylic acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, erucic acid and the like are used. These fatty acids may be used alone or in combination of two or more, depending on the composition required for the product. Since the fatty acids obtained from natural fats and oils are usually a mixture, they are used as a mixture as long as there is no need to use a single product. The fatty acid must be liquid under the reaction conditions, ie its melting point must be below the reaction temperature. When the melting point of fatty acid is high, it is necessary to use an enzyme having high thermostability. Further, depending on the case, the melting point can be lowered by slightly mixing another fatty acid.

The sugar or sugar alcohol and the fatty acid are thoroughly mixed and subjected to the reaction as a homogeneous mixture. When a fatty acid that is solid at room temperature is used, it is preferable that the fatty acid is dissolved by heating and used as a liquid for the reaction. The molar ratio of the sugar or sugar alcohol to be subjected to the reaction and the fatty acid may be appropriately determined according to the desired composition of the product. Usually, an equimolar or more fatty acid is used in order to keep the reaction raw material in a fluid state and to accelerate the reaction of sugar or sugar alcohol.

In a preferred embodiment of the present invention, the sugar or sugar alcohol is mixed with the fatty acid in the form of an aqueous solution, particularly an aqueous solution having a saturated concentration. Enzyme (and, if necessary) water is added to this raw material mixture, and the mixture is allowed to react with stirring under reduced pressure while maintaining a predetermined temperature. Water is 5 to 30% by weight, preferably 10 to 10 based on the total amount of sugar or sugar alcohol and fatty acid.
It is made to exist so that it may be 20 (weight)%. The amount of water is 5%
Even if the amount is less than or equal to 30% or more, the reaction can be carried out, but it is not advantageous in operation.

As the hydrolase capable of degrading fats and oils, various animal-derived and microbial-derived hydrolyzing enzymes are known, as described in the above-mentioned documents, and are commercially available. Any of these can be used. For example, Candida cylindr
acea, Aspergillus niger, Muc
or miehei, Rhizopus deleme
Bacillus subt, a lipase obtained from r
Those derived from microorganisms such as protease obtained from ilis and those derived from animals such as lipase obtained from porcine pancreas are used. Enzyme is usually 0.01 to the reaction raw material
-1% by weight is added, but the reaction will of course proceed outside this range. The reaction temperature is preferably the optimum temperature of the enzyme used. For example, Candida cylindra
It is preferable to carry out the reaction at about 40 ° C. with an enzyme derived from cea or Aspergillus niger. The enzyme can also be used as an immobilized enzyme, and if the thermostability of the enzyme is improved by the immobilization, the reaction can be performed at a temperature higher than the optimum temperature inherent to the enzyme.

The reaction is carried out under reduced pressure, ie with the water being removed by evaporation. The reaction is usually performed under a pressure of 1 to 100 mmHg, preferably 5 to 50 mmHg.
Water is lost by evaporation when the reaction is performed under reduced pressure,
If the amount of remaining water is very small, the reaction rate will decrease. In the present invention, water is added to the reaction system when the reaction rate decreases. Surprisingly, the addition of water restores the reaction rate. The amount of water added is arbitrary, but it is usually advantageous in operation to add it in an amount of 5 to 30% by weight based on the total amount of the reaction raw material and the produced ester. The preferable addition amount is 10 to 20 (weight)%. Water may be added each time the reaction rate decreases. That is, water is added when the reaction product is analyzed over time to track the change in reaction rate over time, and when the reaction rate is below a predetermined value. However, as a simple method, a relational expression such as a reaction time and a reaction rate or a water content of the reaction product and a reaction rate may be obtained by a model experiment or the like, and the addition timing of water may be determined based on the relational expressions. Although it depends on the reaction temperature, pressure, and the amount of water added per time, it is usually sufficient to add water every 1 to 10 hours.

The reaction time is arbitrary, but is usually several hours to several tens hours. After completion of the reaction, the reaction mixture is treated according to a conventional method to obtain the produced ester. For example, the mixture is extracted with a mixed solution of an organic solvent and an alkaline aqueous solution to separate the ester from unreacted fatty acid and sugar or sugar alcohol.

[0013]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

(Example 1) 30.5 g of erythritol
(0.25 mol) dissolved in 50 ml of water, 282 g (1 mol) of oleic acid and Candida cyl
1 g of an enzyme derived from Indracea (manufactured by Amano Pharmaceutical Co., Ltd.) was charged into a reactor equipped with a stirrer, and the reaction was carried out at 40 ° C. under a pressure of 10 mmHg. 50 ml of water was added every 5 hours and the reaction was continued for 15 hours. 300 g of the product was mixed with methyl ethyl ketone and 0.1N aqueous sodium hydroxide solution 1:
The mixture was extracted with 1 liquid mixture to obtain an aqueous phase containing unreacted erythritol and oleic acid and a methyl ethyl ketone phase containing ester. The methyl ethyl ketone phase was concentrated to obtain 120 g of a white paste ester. The weight composition of this ester is about 10% monoester and about 5 diesters.
It was 0% and about 40% of triester.

Example 2 Sorbitol 73 g (0.4
Oleic acid 282
g (1 mol) and Aspergillus niger
1 g of the derived enzyme (Amano Pharmaceutical Co., Ltd. product) was placed in a reactor equipped with a stirrer, and the reaction was carried out at 40 ° C. under a pressure of 40 mmHg. 50 ml of water was added every 6 hours and the reaction was continued for 18 hours. 340 g of the product was extracted with a 1: 1 mixed solution of isobutyl alcohol and 0.1N-sodium hydroxide aqueous solution to recover an isobutyl alcohol phase containing an ester. This is concentrated to a white paste ester 200.
g was obtained. The weight composition of this ester is about 30% monoester, about 50% diester, about 20 triester.
%Met.

Example 3 A solution prepared by dissolving 171 g (0.5 mol) of sucrose in 100 ml of water and lauric acid 20
0 g (1 mol) and Candida cylindrac
1 g of an enzyme derived from ea (manufactured by Amano Pharmaceutical Co., Ltd.) was placed in a reactor equipped with a stirrer and reacted at 40 ° C. under a pressure of 10 mmHg. 50 ml of water was added every 5 hours and the reaction was continued for 15 hours. 350 g of the product was extracted with a 1: 1 mixture of methyl ethyl ketone and a 0.1 N-sodium hydroxide aqueous solution to recover a methyl ethyl ketone phase containing an ester. This is concentrated to give 250 g of white paste ester.
Got The weight composition of this ester is about 2 monoesters.
0%, diester about 45%, triester about 35%
Met.

(Comparative Example 1) The procedure of Example 2 was repeated except that water was not added during the reaction.
The reaction was carried out for 8 hours. 330 g of the product was post-treated in the same manner as in Example 2 to obtain 75 g of a white paste ester.

[0018]

EFFECTS OF THE INVENTION According to the present invention, an ester can be produced with high productivity without precisely controlling the water content in the reaction system.

Claims (1)

[Claims] 1. A method for producing an ester by reacting a sugar or sugar alcohol with a fatty acid in the presence of a hydrolase capable of degrading fats and oils, wherein in the reaction, water is intermittently added to the reaction system under no solvent and under reduced pressure. A method characterized by carrying out while adding.