KR100463743B1 - Separation Method Of Unsaturated Fatty Acid And Composition Of Oil And Fat Containing Diglyceride Prepared With The Separated Fatty Acid - Google Patents

Abstract

The present invention relates to a method for separating unsaturated fatty acids and to high diglyceride-containing fat and oil compositions prepared using the separated fatty acids. More specifically, from the fatty acid mixture derived from vegetable oil, saturated fatty acid crystals are formed in a batch or continuous cooling crystal method without any additives, and then a liquid part containing unsaturated fatty acid and a crystal part containing saturated fatty acid are obtained. It relates to a method for separating high-purity unsaturated fatty acids, and to oil-containing compositions containing high diglycerides produced by ester synthesis reactions of fatty acids and glycerol separated above.

Description

Separation Method Of Unsaturated Fatty Acid And Composition Of Oil And Fat Containing Diglyceride Prepared With The Separated Fatty Acid}

The present invention relates to a method for separating unsaturated fatty acids and to high diglyceride-containing fat and oil compositions prepared using the separated fatty acids. More specifically, the saturated fatty acid crystals are formed from a fatty acid mixture derived from vegetable oil by a batch or continuous cooling crystal method without any additives, and then a liquid part containing unsaturated fatty acid and a crystal part containing saturated fatty acid are obtained. A method for separating fatty acids and a liquid oil-fat composition containing diglycerides produced by the ester synthesis reaction of unsaturated fatty acids and glycerol separated above.

Plant oil and fat is generally composed of triglyceride (triglyceride) in the form of three molecules of fatty acid combined with one molecule of glycerol. In general, fats and oils are classified into a solid phase and a liquid phase, depending on whether they exist in a solid state or a liquid state at room temperature. Triglycerides rich in saturated fatty acids having high melting points are more likely to exist in solid phase at room temperature, and triglycerides rich in unsaturated fatty acids having low melting point are likely to exist in liquid phase at room temperature. On the other hand, diglyceride, which is naturally present in a small amount, does not increase triglyceride content in the body because it contains less fatty acid in triglyceride and is not resynthesized into triglyceride when digested and absorbed in vivo. There is a physiological effect that does not accumulate. Because of this, diglycerides are widely used in the field of functional foods, pharmaceuticals and cosmetics.

Diglycerides can typically be prepared by the esterification of glycerol with fatty acids or the alcohol exchange reaction of glycerol with fats and oils. Korean Patent Publication No. 2001-35226, Korean Patent Publication No. 2001-92006 and Korean Patent Publication No. 2001-35226 are oil-fat compositions containing a high content of diglyceride by adding 1,3-position specific lipase to fats and oils. The manufacturing method of has been disclosed.

However, since the oil-fat composition containing the diglyceride produced by the said method is a form in which saturated fatty acid and unsaturated fatty acid are mixed, it is conventionally difficult to maintain a liquid form at room temperature. In addition, compared to saturated fatty acids, unsaturated fatty acids are essential fatty acids that are not synthesized in the body in animals, and have a physiological effect of reducing blood cholesterol. Recently, many methods for separating saturated fatty acids and unsaturated fatty acids derived from vegetable oils have been developed. Korean Patent No. 262422 and Korean Patent Publication No. 2001-8387 disclose a method of separating and purifying unsaturated fatty acids of high purity by the urea addition crystallization method of adding methanol and urea to vegetable oil. Korean Patent Laid-Open Publication No. 2002-42432 discloses a method of separating unsaturated fatty acids of interest with high purity by using urea addition crystallization, cooling crystallization, and solid-liquid chromatography. In addition, International Patent Publication No. 99/7812 discloses a method of separating unsaturated fatty acids by adding an emulsifier to a raw fatty acid mixture, cooling the same, and drying and removing the crystal part.

However, such a method requires the use of separate additives such as organic solvents and emulsifiers for the separation of unsaturated fatty acids. Therefore, the fatty acids thus produced are disadvantageous in that they are inadequate to be applied to foods and are inexpensive in terms of manufacturing cost. When the emulsifier is added, the emulsifier remains in the final product, which may affect physical properties and texture when applied to food.

Accordingly, the present inventors have developed a method for separating unsaturated fatty acids of high purity by cooling crystallization under specific conditions without using separate additives such as an organic solvent or an emulsifier while studying a method for separating unsaturated fatty acids. The present invention has been completed by preparing a liquid fat or oil containing a high content of diglycerides using fatty acids.

Accordingly, it is an object of the present invention to provide a method for separating unsaturated fatty acids.

Another object of the present invention is to provide a liquid fat or oil composition comprising a diglyceride prepared using the separated fatty acid.

Figure 1 shows the separation of unsaturated fatty acids by the batch cooling crystal method according to the present invention.

Figure 2 shows the separation of unsaturated fatty acids by the continuous cooling crystal method according to the present invention.

In order to achieve the above object, the present invention is characterized in that the saturated fatty acid crystals are formed from the raw fatty acid mixture by a cooling crystal method without any additives, and then separated into a liquid part containing unsaturated fatty acid and a crystal part containing saturated fatty acid. It provides a method for separating unsaturated fatty acids.

More specifically, the present invention provides a separation method by a batch cooling crystal method or a continuous cooling crystal method.

The batch cooling crystallization method (a) dissolves the raw fatty acid mixture at 50-90 ° C., cools it to 10-25 ° C., and injects it into the primary crystallization tank to stir saturated fatty acid crystals while stirring at 5-10 rpm for 30 minutes to 4 hours. Forming to obtain a first crystal complete solution;

(b) by mixing 10 to 40% by weight of the first crystal complete solution obtained in step (a) with 60 to 90% by weight of the raw fatty acid mixture to suppress the solidification of the crystal complete solution and unsaturated adsorbed to saturated fatty acid crystal nuclei Removing nuclei of fatty acids;

(c) The mixed solution of (b) was cooled to -5 to 5 ° C, injected into a secondary crystallization tank, and saturated fatty acid crystals were grown while stirring at 5 to 20 rpm for 1 to 20 hours to prepare a secondary crystal complete solution. Obtaining; And

(d) filtering the secondary crystal complete solution obtained in step (c) to separate the crystal part containing saturated fatty acid and the liquid part containing unsaturated fatty acid.

Continuous cooling crystal method

(a) Dissolve the raw fatty acid mixture at 50-90 ° C. and cool it to 10-25 ° C., which is a volume velocity of 0.25-2 CTV / hr (CTV: Crystallizing Tank Volume) in the primary crystallization tank. Injecting to form a saturated fatty acid crystal nucleus while stirring at 5 ~ 10rpm to obtain a primary crystal completion solution;

(b) by mixing 10 to 40% by weight of the first crystal complete solution obtained in step (a) with 60 to 90% by weight of the raw material fatty acid mixture to suppress the solidification of the crystal complete solution and unsaturated adsorbed to saturated fatty acid crystal nuclei Removing nuclei of fatty acids;

(c) The mixed solution of (b) was cooled to -5 to 5 ° C and injected into the secondary crystallization tank at a volume rate of 0.05 to 1 CTV / hr, and saturated fatty acid crystals were grown while stirring at 5 to 20 rpm. Obtaining a completion solution;

(d) 0.5 to 8.0% by weight of the secondary crystal complete solution obtained in step (c) is circulated to the primary crystallization tank of step (a), and the remaining 92 to 99.5% by weight is filtered to contain saturated fatty acid. Separating the crystalline portion and the liquid portion containing unsaturated fatty acid; And

(e) mixing the secondary crystal complete solution and the raw fatty acid mixture circulated in the step (d) in a ratio of 5 to 20% by weight: 80 to 95% by weight to obtain saturated fatty acid crystal nuclei in the same manner as in step (a). It is characterized by consisting of successive steps to form.

In order to achieve another object of the present invention, the present invention provides a liquid fat or oil composition containing 80 to 99% by weight of diglyceride prepared by the ester synthesis reaction of the unsaturated fatty acid separated according to the above method.

Hereinafter, the present invention will be described in detail.

The unsaturated fatty acid separation method of the present invention is a high-purity unsaturation by the cooling crystal method under conditions that can suppress the progression of solidification that may occur during the crystallization of fatty acids without using an additive such as an organic solvent or an emulsifier from the raw fatty acid mixture. It is characterized by the separation of fatty acids.

Raw fatty acid mixture

Raw fatty acid mixtures can be obtained by hydrolyzing plant fats and converting them to fatty acids. Plant fats and oils include, but are not limited to, fats containing unsaturated fatty acids such as rapeseed oil, soybean oil, jade oil, palm olein oil, cottonseed oil, sunflower oil, safflower oil and brown rice oil.

As a method of hydrolyzing the vegetable oil to obtain a fatty acid mixture, an enzyme such as a non-specific lipase or a catalyst such as sodium hydroxide may be used. In one embodiment of the present invention, water and lipase were added to the vegetable oil and hydrolyzed at a constant temperature for a predetermined time, and 90% or more of fatty acids could be obtained by layer separation or centrifugation.

Batch Cooling Crystallization

Batch cooling crystallization means that the process proceeds closed within a certain raw material range without additional raw material supply. The batch cooling crystallization method forms a saturated fatty acid crystal nucleus from the raw fatty acid mixture, and further dilutes the raw fatty acid mixture to prevent solidification of the crystal complete solution including the saturated fatty acid crystal nuclei and adsorbed to the saturated fatty acid crystal nuclei. After removing the crystal nuclei of unsaturated fatty acids and growing saturated fatty acid crystals, the crystal complete solution is filtered to separate the liquid portion containing unsaturated fatty acids and the crystal portion containing saturated fatty acids (FIG. 1). The batch cooling crystallization method will be described step by step.

In the step (a), the raw fatty acid mixture is heated to a temperature of 50 to 90 ° C. using a heat exchanger to make it completely liquid, and then cooled to 10 to 25 ° C., preferably 15 to 20 ° C. At temperatures above 25 ° C., almost no crystals are formed in the primary crystal nucleation process, and at temperatures below 10 ° C., solidification occurs due to sudden expansion of the crystals. The fatty acid mixture adjusted to a suitable temperature is placed in a primary crystallization tank, and saturated fatty acid crystal nuclei are formed while stirring at 5 to 10 rpm for 30 minutes to 4 hours, preferably for 30 minutes to 1 hour, thereby completing the primary crystal completion solution. To obtain. On the other hand, if the primary crystallization time is less than 30 minutes, the amount of crystal nuclei is too small, the crystal recovery rate of saturated fatty acids is low in the subsequent crystal growth process. If the primary crystallization time is 4 hours or more, excessive crystallization (solidification) causes the flow to be no longer difficult to crystallize.

In step (b), by mixing and diluting 10-40% by weight of the primary crystal complete solution in which crystal nuclei are formed in step (a) with 60-90% by weight of the raw material fatty acid mixture, the crystal complete solution is prevented from being solidified and saturated fatty acid The unsaturated fatty acid crystal nuclei adsorbed on the crystal nuclei are removed. This is because unsaturated fatty acid crystal nuclei can be generated in addition to saturated fatty acid crystal nuclei under the same conditions as in step (a). That is, in the case of oleic acid among unsaturated fatty acids, crystals may be formed at temperatures lower than the melting point of 13.4 to 16.3 ° C. In addition, when present in a mixture with saturated fatty acids, the melting point may be increased, and unsaturated fatty acids may be crystallized (co-authored by fatty acid chemistry 2nd edition, Inaba, Hirano, published by Shinseobang, 62-63p (1997)). Therefore, the present inventors have a possibility that a small amount of unsaturated fatty acids can be crystallized in step (a), and further, by injecting a raw material fatty acid mixture to dilute the primary crystal complete solution to suppress the solidification and at the same time the crystallized unsaturated fatty acids Removed

In step (c), the mixture of step (b) is cooled to -5 to 5 ° C, preferably 0 to 3 ° C, and injected into a secondary crystallization tank by using a heat exchanger for 30 minutes to 20 hours, preferably A secondary crystal completion solution is obtained by stirring at 5-20 rpm with a paddle type stirrer for 30 minutes to 4 hours to allow crystals of saturated fatty acid to grow. If the secondary crystallization time is 20 hours or more, excessive crystallization (solidification) causes the flow to be no longer difficult to crystallize.

In step (d), the secondary crystal complete solution obtained in step (c) is separated into a crystal part containing saturated fatty acid and a liquid part containing unsaturated fatty acid at 0 to 5 ° C. using a press filter or a drum filter. The liquid portion contains 90 to 99% by weight of unsaturated fatty acid content in high purity.

Continuous Cooling Crystallization

The continuous cooling crystallization method is based on the batch cooling crystallization method, so that the temperature control and crystallization time during the process are set to a volume velocity according to the size of the crystallization tank so that raw materials do not stay in the tank so that one process and the next fixing are not disconnected in time. The concept is to make the process more efficient by injecting or discharging it into the container. Therefore, the continuous cooling crystallization method of the present invention forms a saturated fatty acid crystal nucleus to obtain a first crystal complete solution, and the mixture of the raw fatty acid mixture is diluted therein to grow saturated fatty acid crystal nuclei therefrom, thereby completing secondary crystallization. After obtaining a liquid, a part of it was circulated to prepare a crystal nucleus, and the remaining crystal growth liquid was filtered to separate the crystal part from the liquid part, and a portion of the circulated crystallized solution and the raw material fatty acid mixture were mixed at a constant ratio to saturate. It is a method for forming a fatty acid crystal nucleus is performed continuously (Fig. 2). The continuous cooling crystal method will be described in more detail as follows.

In the step (a), the raw fatty acid mixture is heated to a temperature of 50 to 90 ° C. using a heat exchanger to make it completely liquid, and then cooled to 10 to 25 ° C., preferably 15 to 20 ° C. At temperatures above 25 ° C., almost no crystals are formed in the primary crystal nucleation process, and at temperatures below 10 ° C., solidification occurs due to sudden expansion of the crystals. The fatty acid mixture adjusted to the appropriate temperature is injected into the primary crystallization tank at a volume rate of 0.25-2 CTV / hr (CTV: Crystallizing Tank Volume), preferably at a volume rate of 0.5-1 CTV / hr. By passing through the primary crystallization tank so that crystal nuclei of saturated fatty acid are formed, a primary crystal complete solution is obtained. At this time, the paddle type stirrer mounted in the crystallization tank is stirred at 5 ~ 10rpm. On the other hand, the volume velocity of 2CTV / hr or more means that the residence time in the crystallization tank is 30 minutes or less, so that the amount of crystal nuclei is too small, and the crystal recovery rate of saturated fatty acid is low during subsequent crystal growth, The volume velocity becomes longer than 4 hours so that the crystallization cannot continue because of excessive crystallization (solidification).

In step (b), 10 to 40% by weight of the first crystal complete solution of step (a) and 60 to 90% by weight of the raw material fatty acid mixture are mixed and diluted to prevent the crystal complete solution from solidifying and adsorbed onto saturated fatty acid crystal nuclei. Remove unsaturated fatty acids.

In step (c), the mixed solution of (b) is cooled to -5 to 5 ° C, preferably 0 to 3 ° C by using a heat exchanger, and a volume velocity of 0.05 to 1 CTV / hr in the secondary crystallization tank, preferably 0.25 A secondary crystal completion solution is obtained by growing saturated fatty acid crystals by injecting at a volume rate of ˜0.5 CTV / hr. At this time, using a paddle type stirrer attached to the secondary crystallization tank is stirred at 5 ~ 20rpm. On the other hand, when injecting at a volume velocity of 1 CTV / hr or more, the residence time in the secondary crystallization tank is less than 1 hour, so that crystal growth is hardly achieved, resulting in low crystal recovery rate of saturated fatty acids. In the case of injection at a volume velocity of 0.025 CTV / hr or less, the residence time in the secondary crystallization tank is more than 20 hours, so that the flow is difficult to continue and crystallization cannot be continued.

Step (d) circulates 0.5 to 8.0% by weight of a part of the secondary crystal completion solution obtained in step (c) to the primary crystallization tank of step (a), and the remaining 92 to 99.5% by weight is filtered and saturated. The step of separating into a crystal part containing a fatty acid and a liquid part containing an unsaturated fatty acid.

In step (e), the secondary crystal complete solution circulated in step (d) and the raw material fatty acid mixture are mixed at a ratio of 5 to 20% by weight: 80 to 95% by weight to obtain crystal nuclei in the same manner as in step (a). It consists of successive steps to form.

Unsaturated fatty acid having a high saturated fatty acid content of 60 to 80% by weight and 90 to 99% by weight of unsaturated fatty acid, preferably about 93 to 95% by weight, according to the batch or continuous cooling crystal method of the present invention. A fatty acid high content liquid part can be obtained.

Preparation of Diglyceride-Containing Oil-Based Composition

The high diglyceride-containing fat and oil composition can be prepared according to the present invention by an ester synthesis reaction of a liquid portion containing high unsaturated fatty acid or a crystal part containing high saturated fatty acid with glycerol. The ester synthesis reaction can be carried out by a chemical method of adding an alkali catalyst and a biological method using a lipase enzyme, all of which are known. Preferably it may be carried out by a biological method using a lipase enzyme. As lipase enzymes, conventionally known 1,3-position-specific lipases are used. 1,3-position-specific lipases are not particularly limited and include, for example, microorganisms such as Rhizopus sp. Microorganisms, Aspergillus sp. Microorganisms and Mucor sp. Microorganisms. Lipase or pancreatic lipase can be used. In one embodiment of the present invention, 1,3-position-specific lipase (Lipozyme IM) was purchased from Novo Nordisk. Diglycerides can be prepared according to known methods using the lipase (Korean Patent Publication No. 2001-92006, Japanese Patent Publication No. 64-71495, and Korean Patent Publication No. 2001-35226).

When the ester synthesis reaction is completed, the liquid oil-based composition having a diglyceride content of 80 to 99% by weight may be recovered through a purification process such as molecular distillation, decolorization, and deodorization. In one embodiment of the present invention, the liquid-phase oil-fat composition of the present invention showed an unsaturated fatty acid content of about 90-95%, and it was found that the melting point was about -2 ° C. to maintain the liquid state very stably at room temperature. .

The liquid diglyceride-containing fat or oil composition of the present invention can be used for salad oil or fried oil.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

<Example 1>

Isolation of Unsaturated Fatty Acid from Batch-Derived Fatty Acid by Batch Cooling Crystallization

10 kg (9,270 ml) of soybean oil, 10 kg of water, 6 g of lipase OF (manufactured by Meitosan Co., Ltd.) were placed in a 30 L container, heated to 37 DEG C, hydrolyzed for 20 hours, and separated by 50 DEG C to obtain a fatty acid portion as an upper layer. The obtained fatty acid was analyzed according to the Association of Official Analytical Chemists (AOAC) test method. As a result, saturated fatty acid was 16.1% and unsaturated fatty acid was 83.9%. 500 g of the obtained fatty acid was completely dissolved in a liquid phase while being heated to 55 ° C., cooled to 15 ° C., placed in a primary crystallization tank (volume 10 L), and stirred at 10 rpm (paddle type stirrer) for 1 hour to produce saturated fatty acid crystal nuclei. Prepared. At this time, as the primary crystallization tank was made of stainless, it was used that was kept warm and paddle type stirrer. The raw fatty acid mixture obtained by hydrolysis was cooled to 15 ° C., and 4.5 kg was injected and mixed to prevent solidification and to remove the unsaturated fatty acid crystal nuclei adsorbed onto the saturated fatty acid crystal nuclei. The mixture was cooled to 0 ° C. and then crystallized with stirring at 5 rpm for 4 hours. The crystal complete solution was then filtered at 3 ° C using a press filter to separate the high unsaturated fatty acid-containing liquid portion and the high saturated fatty acid-containing crystal portion. The recovery rate of the liquid phase portion was expressed as the ratio of the liquid portion recovery amount to the total amount. As a result, the liquid portion recovery rate (liquid recovery amount ÷ total amount) 67%.

<Example 2>

Separation of Unsaturated Fatty Acids from Soybean Oil-Derived Fatty Acids by Continuous Cooling Crystallization

The fatty acid obtained by the method of Example 1 was completely dissolved in the liquid phase while warming to 55 ° C, and then cooled to 15 ° C in a primary crystallization tank (volume 1,000ml) at a volume rate of 1,000 ml / hr (1 CTV / hr). Fatty acid crystal nuclei were prepared by injecting with stirring (paddle type stirrer). At this time, the primary crystallization tank was made of a stainless material and insulated, and the inlet and outlet were made of transparent silicon tubing having a diameter of 6 mm, and a paddle type stirrer was used. When the primary crystallization tank is completely filled to obtain the primary crystallization completion liquid, it is transferred to a 5 L mixing tank using a pump connected at the same speed as the above injection volume rate (1,000 ml / hr, 1 CTV / hr) and simultaneously The raw material fatty acid mixture at 15 ° C. was injected at a volume rate of 4,000 ml / hr to prevent solidification, and the adsorption portion of unsaturated fatty acids was diluted from saturated fatty acid crystal nuclei. The mixture was cooled to 0 ° C. using a heat exchanger and then injected into the secondary crystallization tank (volume 20 l) at 5 rpm at a volume rate of 5 l / hr with stirring. At this time, the secondary crystallization tank is made of stainless steel and kept warm, the inlet and outlet is made of transparent silicone tubing having a diameter of 12mm and was used with a paddle type stirrer. Once the secondary crystallization tank is fully filled to obtain the secondary crystal completion liquid, 4,900 ml / hr is transferred to the filtration tank using a pump connected at the same rate as the total injection volume rate (5 l / hr), and 100 ml / hr Was circulated to the primary crystallization tank. The secondary crystal completed liquid transferred to the filtration tank was separated into a liquid part containing unsaturated fatty acid and a crystal part containing saturated fatty acid by filtration at 3 ° C. using a press filter. In addition, the raw fatty acid mixture was continuously injected into the primary crystallization tank at a volume rate of 900 ml / hr, and the secondary crystal complete solution circulated above was injected at a volume rate of 100 ml / hr to continuously saturate fatty acid crystal nuclei. Formed. As a result, the liquid phase recovery rate (liquid recovery amount ÷ total amount) was 69% by weight.

<Example 3>

Separation of Unsaturated Fatty Acids from Continuous Oil-Derived Fatty Acids by Rapeseed Oil

Hydrolyzed and layered from the rapeseed oil in the same manner as in Example 1 to obtain a fatty acid. The fatty acid composition obtained was 8.2% saturated fatty acid and 91.8% unsaturated fatty acid. The fatty acid was injected into the primary crystallization tank at a volume rate of 1,200 ml / hr, and the crystallization liquid was injected at a volume rate of 300 ml / hr. At this time, the injection temperature of the primary crystallization tank was adjusted to 20 ° C. and then mixed. Raw fatty acid was injected into the tank at a volume rate of 3,500 ml / hr, and cooling crystallization was carried out at the injection temperature of the secondary crystallization tank at 3 ° C. All other conditions were performed similarly to Example 2. As a result of the experiment, the recovery of the liquid part was 76% as shown in Table 1.

<Example 4>

Separation of Unsaturated Fatty Acids from Continuous Oil Crystals from Fatty Acids Derived from Oak Oil

The fatty acid was obtained by hydrolysis and layer separation from the jade oil in the same manner as in Example 1. The fatty acid composition obtained was 15.2% saturated fatty acid and 84.8% unsaturated fatty acid. The fatty acid was injected into the primary crystallization tank at a volume rate of 1,900 ml / hr, and the crystallization liquid was injected at a volume rate of 100 ml / hr. At this time, the injection temperature of the primary crystallization tank was adjusted to 12 ° C. and mixed. Raw fatty acid was injected into the tank at a volume rate of 3,000 ml / hr, and cooling crystals were carried out at an injection temperature of the secondary crystallization tank at -2 ° C. All other conditions were performed similarly to Example 2. As a result of the experiment, the recovery of the liquid phase was 65% as shown in Table 1.

Comparative Example 1

Separation of Unsaturated Fatty Acids by Continuous Cooling Crystallization with Different Primary Crystallization Tank Injection Temperature

From soybean oil was hydrolyzed and layered in the same manner as in Example 1 to obtain a fatty acid. All conditions were carried out in the same manner as in Example 2 and the primary crystallization tank injection temperature was adjusted to 5 ℃. As a result of the experiment, the solidified solution was unable to be discharged.

Comparative Example 2

Separation of Unsaturated Fatty Acids by Continuous Cooling Crystallization with Different Primary Crystallization Tank Injection

From soybean oil was hydrolyzed and layered in the same manner as in Example 1 to obtain a fatty acid. All conditions were carried out in the same manner as in Example 2, and operated in a state in which the primary crystallization tank was filled with only 250 ml of fatty acid raw material (primary crystallization injection volume rate of 2.5 CTV / hr). As a result of the experiment, the recovery of the liquid portion was 80% as shown in Table 1.

Comparative Example 3

Separation of Unsaturated Fatty Acids by Continuous Cooling Crystallization with Different Secondary Crystallization Tank Injection Temperature

From soybean oil was hydrolyzed and layered in the same manner as in Example 1 to obtain a fatty acid. All conditions were carried out in the same manner as in Example 2 and the secondary crystallization tank injection temperature was adjusted to 8 ℃. As a result of the experiment, the recovery of the liquid part was 85% as shown in Table 1.

Comparative Example 4

Separation of Unsaturated Fatty Acids by Continuous Cooling Crystallization with Different Injection Volume of Secondary Crystallization Tank

From soybean oil was hydrolyzed and layered in the same manner as in Example 1 to obtain a fatty acid. All the conditions were carried out in the same manner as in Example 2 and was operated in the state of filling only 4,000ml of raw material in the secondary crystallization tank. As a result of the experiment, the recovery of the liquid portion was 86% as shown in Table 1.

Recovery of Liquid Part According to Operating Conditions in Cooling Crystallization Process Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Raw material maintenance name Soybean oil Soybean oil Rapeseed oil Jade oil Soybean oil Soybean oil Soybean oil Soybean oil Operating conditions Hydrolyzed Fatty Acid Composition Saturation ¹⁾ 16.1 16.1 8.2 15.2 16.1 16.1 16.1 16.1 Unsaturated ²⁾ 83.9 83.9 91.8 84.8 83.9 83.9 83.9 83.9 Primary crystallization injection temperature (℃) 15 15 20 10 5 15 15 15 Primary crystallization raw material weight ratio ³⁾ 9: 1 9: 1 8: 2 9.5: 0.5 9: 1 9: 1 9: 1 9: 1 Primary Crystallization Injection Volume Speed (CTV / hr) Stir for 30 minutes ⁶⁾ One 1.5 2 One 2.5 One One Mixing weight ratio of mixing step ⁴⁾ 2: 8 2: 8 3: 7 4: 6 Solidified in primary crystallization tank. 2: 8 2: 8 2: 8 Second Crystallization Injection Temperature (℃) 0 0 3 -2 0 8 0 Secondary Crystallization Injection Volume Speed (CTV / hr) 4 hours stirring ⁶⁾ 0.25 0.25 0.25 0.25 0.25 0.25 Liquid recovery rate (%) ⁵⁾ 67 69 76 65 80 85 86

1) Saturated fatty acid composition: C _{16: 0} + C _{18: 0}

2) Unsaturated fatty acid composition: C _{18: 1} + C _{18: 2} + C _{18: 3}

3) The ratio of the amount of raw fatty acid and the amount of crystal completion

4) Ratio between the amount of primary crystal completion and the amount of raw fatty acid

5) Liquid recovery amount ÷ total amount

6) The batch cooling crystallization method shows the crystallization time instead of the volume velocity.

Example 5

Preparation of Diglyceride-Containing Fat or Oil Composition Using Separate Fatty Acids

Diglycerides are obtained by mixing the liquid part containing the unsaturated fatty acid obtained in Examples 1 to 4 and Comparative Examples 2 to 4 with glycerol and performing an ester synthesis reaction using 1,3-position specific lipase under vacuum drying. A finite liquid fat and oil composition was prepared. That is, 794 g of the liquid phase obtained in each Example, 129 g of glycerol, and 24 g of 1,3 position-specific lipase (Lipozyme IM, manufactured by Novo Nordisk) were reacted at 45 ° C. under reduced pressure at 5torr for 10 hours. The diglyceride high oil-fat composition obtained here was molecular distillation and decolorization deodorization. The glyceride composition of the prepared fats and oils was separated by thin layer chromatography, and the TLC / FID method was detected by a flame ionization detector. 1971) was analyzed by the analysis method and the general maintenance test of fats and oils.

As a result of the experiment, as shown in Table 2, all diglyceride contents were found to contain 80% or more, and the fat and fat composition prepared in the liquid parts of Examples 1 to 4 contained 90% or more of all unsaturated fatty acid contents. appear. In the case of the oil-fat composition prepared from the liquid phase obtained in Comparative Examples 2 to 4, the unsaturated fatty acid content was slightly lower. In addition, the melting point of the final liquid fat and oil composition was lower than that represented by 7 to 8 ℃ when using the liquid portion of the comparative example at -2 ℃ when using the liquid portion of Examples 1 to 4.

From the above experimental results, the recovery rate of the liquid portion in the comparative example was found to be high, but the melting point of the final oil and fat product was found to be higher than the oil and fat product according to the present invention. From this, it was found that when the diglyceride was prepared using the liquid phase part of the present invention separated according to specific conditions, the liquid phase could be more stably maintained.

Physical properties and composition of the liquid fat and oil composition according to the present invention Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 4 Comparative Example 5 Raw material maintenance name Soybean oil Soybean oil Rapeseed oil Jade oil Soybean oil Soybean oil Soybean oil Soybean oil Glyceride Composition (%, w / w) tree 16.3 14.3 17.2 12.3 Solidified in primary crystallization tank. 13.5 15.5 15.2 D 83.3 85.3 82.2 86.5 86.1 83.8 84.1 mother 0.4 0.2 0.5 0.1 0.2 0.5 0.4 fatty acid 0.3 0.2 0.1 0.1 0.2 0.2 0.3 Fatty acid composition (%, w / w) Saturated fatty acid ¹⁾ 5.8 4.8 4.1 4.5 9.8 11.2 11.8 Unsaturated fatty acids ²⁾ 94.2 95.2 95.9 95.5 90.2 88.8 88.2 Melting Point (℃) -2 -2 -2 -2 7 8 8

1) Saturated fatty acid composition: C _{16: 0} + C _{18: 0}

2) Unsaturated fatty acid composition: C _{18: 1} + C _{18: 2} + C _{18: 3}

Separation method of unsaturated fatty acid according to the present invention is the liquid fatty acid and unsaturated part containing high unsaturated fatty acid by crystallizing the saturated fatty acid by batch or continuous cooling crystallization method without using additives such as emulsifier and organic solvent in the raw fatty acid mixture It is very useful for obtaining crystal parts containing high fatty acids. In addition, a liquid fat or oil composition containing high diglycerides can be prepared by ester synthesis reaction of unsaturated fatty acid and glycerol thus obtained. The fat or oil composition according to the present invention is suitable for use as a food, there is an advantage that the form can be kept stable at room temperature.

Claims (7)

A method for separating unsaturated fatty acids, comprising forming a saturated fatty acid crystal from a raw fatty acid mixture by a cooling crystal method without a separate additive, and then separating it into a liquid part containing an unsaturated fatty acid and a crystal part containing a saturated fatty acid. The method of claim 1, wherein the cooling determination method (a) After melting the raw fatty acid mixture at 50-90 ° C., cooling it to 10-25 ° C. and injecting it into the primary crystallization tank to form saturated fatty acid crystal nuclei with stirring at 5-10 rpm for 30 minutes to 4 hours. Obtaining a crystal completion liquid; (b) by mixing 10 to 40% by weight of the first crystal complete solution obtained in step (a) with 60 to 90% by weight of the raw material fatty acid mixture to suppress the solidification of the crystal complete solution and unsaturated adsorbed to saturated fatty acid crystal nuclei Removing nuclei of fatty acids; (c) The mixed solution of (b) was cooled to -5 to 5 ° C, injected into a secondary crystallization tank, and saturated fatty acid crystals were grown while stirring at 5 to 20 rpm for 1 to 20 hours to prepare a secondary crystal complete solution. Obtaining; And (d) a method of batch cooling crystallization comprising the step of separating the secondary crystal complete solution obtained in step (c) into a crystal part containing saturated fatty acid and a liquid part containing unsaturated fatty acid. The method of claim 1, wherein the cooling determination method (a) Dissolve the raw fatty acid mixture at 50-90 ° C. and cool it to 10-25 ° C., which is a volume velocity of 0.25-2 CTV / hr (CTV: Crystallizing Tank Volume) in the primary crystallization tank. Injecting to form a saturated fatty acid crystal nucleus while stirring at 5 ~ 10rpm to obtain a primary crystal completion solution; (b) by mixing 10 to 40% by weight of the first crystal complete solution obtained in step (a) with 60 to 90% by weight of the raw material fatty acid mixture to suppress the solidification of the crystal complete solution and unsaturated adsorbed to saturated fatty acid crystal nuclei Removing nuclei of fatty acids; (c) The mixed solution of (b) was cooled to -5 to 5 ° C and injected into the secondary crystallization tank at a volume rate of 0.05 to 1 CTV / hr, and saturated fatty acid crystals were grown while stirring at 5 to 20 rpm. Obtaining a completion solution; (d) 0.5 to 8.0% by weight of the secondary crystal complete solution obtained in step (c) is circulated to the primary crystallization tank of step (a), and the remaining 92 to 99.5% by weight is filtered to contain saturated fatty acid. Separating the crystalline portion and the liquid portion containing unsaturated fatty acid; And (e) mixing the secondary crystal complete solution and the raw material fatty acid mixture circulated in the step (d) at a ratio of 5 to 20% by weight: 80 to 95% by weight to obtain saturated fatty acid crystal nuclei in the same manner as in step (a). And a continuous cooling crystallization process consisting of successive steps of formation. The method of claim 1 wherein the raw fatty acid mixture is derived from vegetable oil. The method of claim 4, wherein the vegetable oil is selected from the group consisting of rapeseed oil, soybean oil, jade oil, palm olein oil, cottonseed oil, sunflower oil, safflower oil and brown rice oil. The method according to claim 1, wherein the content of unsaturated fatty acid in the liquid portion is 90 to 99% by weight. delete