KR102036556B1 - Method for improving efficiency of enzymatic esterification by using high oleic sunflower oil - Google Patents

Abstract

The present invention relates to a method for improving the efficiency of enzymatic esterification and, more specifically, to a method, in carrying out the reaction for exchanging an acyl group of triacylglyceride with an oleyl group using enzyme, which reduces cost while shortening reaction process time and further improves overall process efficiency and economy by using high-oleic acid sunflower oil as a source of the oleyl oil as a reaction starting material.

Description

Method for improving efficiency of enzymatic esterification by using high oleic sunflower oil

The present invention relates to a method for improving the efficiency of enzymatic esterification, and more particularly, to performing the reaction for exchanging acyl groups of triacylglycerides with oleyl groups using an enzyme, an oleyl group which is a reaction starting material. By using high-oleic acid sunflower oil as a source, the present invention relates to a method that can reduce the reaction process time while reducing costs and further improving the overall process efficiency and economy.

Triacylglycerides fats and oils are very widely used in the food industry, among which 1,3-dioleoyl-2-palmitoyl glycerides (OPO) are breast milk fats. As an important component of nutritional research has been conducted a lot.

Fat compositions containing the major fatty acids that predominantly make up breastmilk fats are found a lot in oils and fats of plant origin, but almost all plant origin glycerides do not have saturated fatty acids in the 2-position. In contrast, palmitic acid, a significant amount of saturated fatty acids in breast milk, occupies the 2-position of glycerides.

Recently, as people's interest in infant health increases, the demand for foods similar to breast milk is increasing.

Innis (Adv. Nutr., 2: 275-283, 2011) describes the structural role of triacylglycerols in the diet of infants.

However, conventional milk powder is a mixture of powdered milk and vegetable oil, and contains little palmitic acid at the 2-position when analyzing the oil component of the milk powder.

Accordingly, the application of a high quality breast milk substitute for the addition of 1,3-dioleoyl-2-palmitoyl glyceride (OPO) containing palmitic acid at 2-position, which is similar in composition to breast milk fat, in milk powder. This is increasing.

Mohamad, et al (Lipase-catalyzed interesterification reactions for human milk fat substitutes production, 2013, 115, 270-285), substituted 1,3-positions of the triacylglycerides with lipase. The study of synthesizing dioleoyl-2-palmitoyl glycerides has been mainly conducted.

Due to the 1,3-position specific reaction properties of the triacylglycerides of lipases, the provision of a glyceride backbone containing saturated fatty acids at the 2-position of the triacylglyceride fats is possible with 1,3-dioleoyl-2-palmi. Important in synthesizing soil glycerides (OPO).

These prior art is to use the enzymatic esterification, but there is a problem of low efficiency of the overall process, high manufacturing cost. Accordingly, there is a need for development of a method for further improving overall process efficiency and economic efficiency in producing 1,3-dioleoyl-2-palmitoyl glyceride (OPO) using enzymatic esterification.

The present invention is to provide a method capable of improving the overall process efficiency and economic efficiency in carrying out a reaction for exchanging an acyl group of triacylglycerides with an oleyl group using an enzyme.

In order to achieve the above technical problem, the present invention, in performing the reaction for replacing the acyl group of the triacylglycerides with oleyl oil using an enzyme, high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight as an oleyl group source Provided is a method of enzymatic esterification, which is used.

According to another aspect of the invention, (1) providing a mixture comprising as the reaction starting materials triacylglycerides and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight, and (2) in step (1) There is provided a process for preparing triglycerides, comprising performing an enzymatic esterification reaction on the obtained mixture to exchange acyl groups of the triacylglycerides with oleyl groups.

According to another aspect of the present invention, as a result of enzymatic esterification of a mixture comprising a fatty component comprising triacylglyceride and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight, acyl of the triacylglyceride Fatty compositions are provided, wherein the group comprises triglycerides exchanged with oleoyl groups.

According to another aspect of the invention, the acyl of the triacylglycerides prepared by enzymatic esterification of a mixture comprising a fatty component comprising triacylglycerides and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight. Powdered milk compositions are provided, wherein the group comprises triglycerides exchanged with oleyl groups.

According to the present invention, in carrying out a reaction for exchanging the acyl group of triacylglyceride with an oleyl group by using an enzyme, it is possible to further improve the overall process efficiency and economic efficiency by reducing the reaction process time. Thus, according to an embodiment of the present invention, it is possible to produce dioleoyl monopalmitoyl glycerides from tripalmitoylglycerides with high efficiency and economically through enzymatic esterification reaction.

Hereinafter, the present invention will be described in detail.

Triacylglycerides used as starting materials for enzymatic esterification in the present invention may be edible oils and fats.

The edible fats and oils can be used as long as it is suitable for edible oils such as vegetable oils or animal fats of liquids or solids, cured oils or transesterified oils of the fats and oils, liquid oils obtained by fractionating the fats and oils and solid fats.

Specific examples of the vegetable oil and fat include corn oil, rapeseed oil, soybean oil, cottonseed oil, palm oil, palm oil, rice bran oil, sesame oil, cacao fat, olive oil and combinations thereof. Specific examples of the animal oil and fat include fish oil, And pork fat, beef fat (beef oil), fat of chicken, and a combination thereof. These edible fats and oils can be used individually or in combination of 2 or more.

In one embodiment, the triacylglycerides may be palm fractionation oil that is fractionated palm oil in vegetable oils and fats.

In one embodiment, the acyl groups present in the triacylglycerides are independently saturated or unsaturated having 4 to 24 carbon atoms, more specifically 12 to 22 carbon atoms, even more specifically 14 to 20 carbon atoms. It may be selected from linear aliphatic acyl groups of. For example, the acyl group present in the triacylglyceride may be independently selected from palmitoyl group, stearoyl group and linoleyl group, preferably palmitoyl group, but is not limited thereto.

In one embodiment, at least one of the acyl groups present in the triacylglycerides is a palmitoyl group, preferably two, more preferably all three palmitoyl groups. That is, in the most preferred embodiment, the starting material triacylglycerides is tripalmitoylglycerides (PPP).

In the present invention, high-oleic acid sunflower oil having an oleic acid content of 70% by weight or more is used as another starting material of the enzymatic esterification reaction. If the oleic acid content of the high-oleic acid sunflower oil is less than 70% by weight, there may be a problem that the efficiency of the enzymatic esterification reaction is lowered.

More specifically, the oleic acid content of the high-oleic acid sunflower oil may be 75% by weight or more, and even more specifically 80% by weight or more. In addition, the oleic acid content of the high-oleic acid sunflower oil may be 95% by weight or less, and more specifically, 90% by weight or less.

The high-oleic acid sunflower oil may further include components such as linoleic acid, palmitic acid and stearic acid in addition to oleic acid.

In one embodiment of the present invention, the mixing ratio of the starting material triacylglycerides to high-oleic acid sunflower oil may be 1: 1 to 1: 7 by weight, more specifically 1: 1 to 1: 5, Even more specifically 1: 1 to 1: 3.

In the present invention, the reaction temperature of the enzymatic esterification reaction may be determined according to the type of enzyme used, and specifically, may be 40 ° C. or higher, 45 ° C. or higher, 50 ° C. or higher, 55 ° C. or higher, or 60 ° C. or higher. 85 ° C. or less, 80 ° C. or less, 75 ° C. or less, 70 ° C. or less, or 65 ° C. or less, but is not limited thereto. In one embodiment, the reaction temperature of the enzymatic esterification reaction may preferably be from 40 ° C. to 80 ° C., more preferably from 55 ° C. to 75 ° C.

As the enzyme of the enzymatic esterification reaction in the present invention, known enzymes can be used without particular limitation. Specifically, Candida Antaxica (Candida Antarctica B), Thermomyses LanuginusThermomyces lanuginose), Reoper's MieRhizomucour miehei), Resopers Delema (Rhizopus delemar), Muko Mie (Mucormiehei), Alkaliness (Alcaligenes sp .), Aspergillus niger (Aspergillus niger), Candida Cylindras (Candida cylindraces), Bucolderia Sephacia (Burkholderia cepacia), Candid (Geotricum candidum) And combinations thereof may be used, but not limited to, esterification enzymes derived from microorganisms.

In one embodiment of the present invention, 100 parts by weight to 3000 parts by weight, or 100 parts by weight to 2000 parts by weight, or 100 parts by weight to 1000 parts by weight of a mixture of reaction starting materials per 1 part by weight of enzyme can be continuously treated without replacing the enzyme. However, more amounts can be continued as long as the activity of the enzyme is maintained. For example, if the enzyme activity is appropriate, the mixture of reaction starting materials per 1 part by weight of the enzyme can be continuously processed without replacing the enzyme at least 500 parts by weight, at least 1000 parts by weight, at least 2000 parts by weight or at least 3000 parts by weight of enzyme. There is no particular limitation, and even up to 10000 parts by weight or more can be processed. According to one preferred embodiment, the mixture throughput of reaction starting materials per 1 part by weight of enzyme can be 1000 parts by weight to 3000 parts by weight.

According to another aspect of the invention, (1) providing a mixture comprising as the reaction starting materials triacylglycerides and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight, and (2) in step (1) There is provided a process for preparing triglycerides, comprising performing an enzymatic esterification reaction on the obtained mixture to exchange acyl groups of the triacylglycerides with oleyl groups.

In the above production method, triacylglycerides and high-oleic acid sunflower oils, and enzymatic esterification reactions as reaction starting materials are as described above.

In one embodiment, the triglyceride prepared according to the preparation method may be a dioleoyl monopalmitoyl glyceride, more specifically 1,3-dioleoyl-2-palmitoyl glyceride (OPO).

The acid value of the triglyceride prepared according to the production method of the present invention is 0.6 or less (for example, 0.1 to 0.6), and the peroxide value is characterized in that 3.0 or less (for example, 0.1 to 3.0).

Here, the number of mg of KOH required to neutralize the free fatty acid contained in 1 g of fats and oils is referred to as an 'acid value', and the milli equivalents of peroxide oxygen converted from milli equivalents of iodine free to 1 kg of fats and oils is referred to as a 'peroxide value'.

The acid value of the triglyceride prepared according to the production method of the present invention may be 0.1 to 0.6, more preferably 0.2 to 0.6, even more preferably 0.38 to 0.58. The peroxide value of the triglyceride prepared according to the production method may be 0.1 to 3.0, more preferably 0.15 to 3.0, even more preferably may be 0.2 to 3.0. The production method according to the present invention effectively reduces the acid value and peroxide value in the fats and oils to ensure the food safety of the fats for edible oil, by using the fats and oils as a food additive or a supplement additive of cooking to increase the taste and flavor of food Can increase nutritional value.

In one embodiment, the ratio of the neutral lipid (PPP, PPO, OPO, etc.) having palmitic acid in the sn-2 position in the triglyceride prepared according to the production method of the present invention is preferably 50 to 90% by weight It may be more preferably 50 to 80% by weight.

According to another aspect of the present invention, as a result of enzymatic esterification of a mixture comprising a fatty component comprising triacylglyceride and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight, acyl of the triacylglyceride Fatty compositions are provided, wherein the group comprises triglycerides exchanged with oleoyl groups.

Further, according to another aspect of the present invention, the triacylglyceride prepared by enzymatic esterification of a mixture comprising a fatty component including triacylglyceride and high-oleic acid sunflower oil having an oleic acid content of at least 70% by weight Powdered milk composition is provided which contains the triglyceride in which the acyl group of was replaced with the oleyl group.

In the fat composition and milk powder composition, triacylglycerides and high-oleic acid sunflower oil, enzymatic esterification reaction, and triglycerides are as described above.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, this is only provided to help the understanding of the present invention, the scope of the present invention is not limited thereto.

[ Example ]

A mixture of superstearin (palmitic acid content: 70 wt% or more) (SS) and high oleic sunflower oil (oleic acid content: 80 wt% or more) (HOSFO) as a reaction starting material (SS: HOSFO mixed weight ratio is 1: 1, 1: 1.5, 1: 2, 1: 2.5, 1: 3) 25 g each was added to a 100 mL Erlenmeyer flask, 2.5 g of enzyme (Novozym 40086) (10% by weight of substrate) was weighed separately, and immediately before the reaction. Was added to the reaction starting material mixture.

The enzymatic esterification reaction was carried out at a stirring speed of 150 rpm in a shaking incubator at which the temperature was set at 55 ° C., and after a certain time (0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4 hours, respectively) after the start of the reaction. 1 mL of the upper portion of the reaction mixture was analyzed. The analysis method is as follows.

1) Neutral lipid carbon number analysis

Neutral lipids are separated by carbon number using gas chromatography, and neutral lipids containing 52 carbon atoms (e.g., C18-C16-C18, C16-C18-C18, etc.) such as SPS, SSP, OPO, OOP , LPL, LLP, OPL, etc.) were analyzed. The results are shown in Table 1 below.

2) sn Fatty acid composition analysis at -2 position

Four hours after the start of the reaction, the fatty acid at the sn-2 position was analyzed by gas chromatography, and the ratio of neutral lipids (PPP, PPO, OPO, etc.) having palmitic acid at the sn-2 position was analyzed. It was confirmed. The results are shown in Table 2 below.

[Table 1] C52 concentration by weight of reaction starting material (wt%)

[Table 2] Sn-2 fatty acid ratio by weight of reaction starting material after 4 hours reaction (wt%)

On the other hand, using the oleic acid (OA) as a starting material (SS: OA mixing weight ratio = 1: 1) instead of high oleic sunflower oil to perform the same enzymatic esterification reaction (Novozym 40086), the concentration of C52 of the reaction mixture for each time zone Was analyzed, and the results are shown in Table 3 below with the results of using high oleic sunflower oil (SS: HOSFO mixing weight ratio = 1: 1).

[Table 3] C52 concentration (weight%) by time when using oleic acid (OA)

As can be seen from Table 3, when high oleic acid sunflower oil was used as a starting material of the enzymatic esterification reaction according to the present invention, it took 1 hour for the C52 concentration to reach 30.6% by weight, whereas oleic acid was used. It took 1.5 hours to reach substantially the same C52 concentration (31.0 wt.%).

That is, according to the present invention, when the high oleic acid sunflower oil is used as the starting material of the enzymatic esterification reaction, the reaction (process) time for reaching the C52 concentration of the same target is reduced as compared with the case of the conventional oleic acid. Indicated.

In addition, in contrast to the raw material cost of using the high oleic sunflower oil (SS + HOSFO (1: 1)) and the cost (raw material ratio) of using the oleic acid (SS + OA (1: 1)), SS + OA ( SS + HOSFO (1: 1) showed a 40.9% cost reduction compared to 1: 1).

Thus, according to the present invention, it has been confirmed that dioleoyl monopalmitoyl glyceride from tripalmitoylglyceride can be produced with high efficiency and economically through enzymatic esterification reaction.

Claims (13)

In carrying out the reaction for converting the acyl group of the triacylglyceride to the oleyl group using an enzyme, a high-oleic acid sunflower oil having an oleic acid content of 75 to 90 wt% is used as the oleyl group source, and the starting material triacylglyceride Enzymatic esterification process, characterized in that the mixing ratio of high-oleic acid sunflower oil is 1: 1 to 1: 3 by weight. The method of claim 1, wherein the acyl groups present in the triacylglycerides are independently selected from palmitoyl groups, stearoyl groups, and linoleyl groups. The method of claim 1, wherein the triacylglyceride is tripalmitoylglyceride. The method of claim 1, wherein the throughput of the reaction starting material mixture per 1000 parts by weight of enzyme is 1000 parts by weight to 3000 parts by weight. (1) providing a mixture comprising as the reaction starting materials triacylglycerides and high-oleic sunflower oil having an oleic acid content of 75 to 90% by weight, and
(2) performing an enzymatic esterification reaction on the mixture obtained in step (1) to exchange acyl groups of the triacylglycerides with oleyl groups,
The mixing ratio of starting material triacylglycerides to high-oleic acid sunflower oil is 1: 1 to 1: 3 by weight,
Method for preparing triglycerides. The process for producing triglycerides according to claim 5, wherein the acyl group present in the triacylglyceride is independently selected from palmitoyl group, stearoyl group and linoleyl group. The method for producing triglyceride according to claim 5, wherein the triacylglyceride is tripalmitoylglyceride. The process for producing triglycerides according to claim 5, wherein the throughput of the reaction starting material mixture per 1 part by weight of enzyme is 1000 parts by weight to 3000 parts by weight. The method for producing triglyceride according to claim 5, wherein the triglyceride prepared is dioleoyl monopalmitoyl glyceride. delete delete delete delete