KR20090035175A - Method for preparing high-purified unsaturated fatty acids - Google Patents

Abstract

A method for manufacturing a highly pure unsaturated fatty acid is provided to mass-produce the highly pure unsaturated fatty acid with a simple and efficient process by removing the saturated fatty acid from the free fatty acid. A method for manufacturing a highly pure unsaturated fatty acid comprises the steps of: (a) preparing pre-activated urea by drying the aqueous urea solution with a vacuum spray dryer; (b) injecting the free fatty acid obtained by hydrolyzing vegetable oil in a reactor; (c) injecting and mixing the pre-activated urea prepared in the (a) step in the reactor of (b) step; (d) removing the saturated fatty acid by filtering the mixture of (c) step; and (d) distilling the free fatty acid filtered in the (d) step.

Description

Method for preparing high purity unsaturated fatty acid {Method for Preparing High-Purified Unsaturated Fatty Acids}

The present invention relates to a method for producing a high-purity unsaturated fatty acid, and more specifically, only active-elements that maximize the reactivity by drying with a vacuum spray dryer without using an organic solvent harmful to humans. The present invention relates to a method for producing a high-purity unsaturated fatty acid that can be used, effectively removes saturated fatty acids, increases the content of physiologically active ingredients as much as possible, and can mass-produce inexpensively in a simpler and more efficient process.

Conjugated linoleic acid (CLA) is known to have excellent effects such as reducing body fat, increasing immunity, anticancer, type 2 antidiabetic, lowering cholesterol, anti-arteriosclerosis, or increasing blood circulation. It is a material that is in the spotlight as a dietary functional food. Such conjugated linoleic acid has several isomers, in particular cis-9, trans-11 C18: 2 (c9, t11 C18: 2) conjugated linoleic acid and trans-10, cis-12 C18: 2 (t10, c12 C18: 2) It has been found that conjugated linoleic acid has the greatest bioactive effect among the isomers of conjugated linoleic acid.

Therefore, the content of c9, t11 C18: 2 conjugated linoleic acid and t10, c12 C18: 2 conjugated linoleic acid will have an absolute effect on the functionality of the conjugated linoleic acid composition, so it is highly desirable to increase the content of the two isomers. More preferably, it is reported to be safe for human body only if the content of c9, t11 C18: 2 conjugated linoleic acid and t10, c12 C18: 2 conjugated linoleic acid is increased and the ratio of both isomers is about 50:50. . In particular, when the content of t10, c12 C18: 2 conjugated linoleic acid is relatively high, functional effects such as body fat reduction are more excellent, but clinical side effects such as triglycerides and glucose levels in the body may be increased. The results were recently reported.

Therefore, the conjugated linoleic acid coexists in the ratio of the content of the two isomers not to deviate from 50:50 while increasing the content of c9, t11 C18: 2 conjugated linoleic acid and t10, c12 C18: 2 conjugated linoleic acid as much as possible, preferably 0.95-1.05. It is more preferred to provide a composition.

Gamma-linoleic acid is known to have an excellent effect on inflammatory immune diseases such as atopic dermatitis or rheumatoid arthritis. Gamma-linolenic acid is a precursor of human anti-inflammatory substances such as prostaglandin and 15-hydroxyeicosa trienoic acid, and especially leukotriene B4 (leukotrien), which is an inflammatory factor when the gamma-linolenic acid is at least 60% pure. B4, LTB4) have been shown to be effective ( Prostaglandins , Leukotrienes ). and Essential Fatty Acids , 65 (4): 205-210 (2001))

In the case of the existing conjugated linoleic acid composition and gamma-linolenic acid composition of borage oil, evening primrose oil, and blackcurrant oil, a large amount of saturated fatty acids such as palmitic acid and stearic acid are present, and the arteries are contained in the conjugated linoleic acid and gamma-linolenic acid composition provided for health. It is more desirable to minimize saturated fatty acids as much as possible, which may cause side effects such as curing or thrombus formation.

US Patent No. 6,762,313 and US Patent No. 7,067,684 disclose a method for increasing the content of conjugated linoleic acid through molecular distillation of a small molecular weight saturated fatty acid, but the method differs from the molecular weight by conjugated linoleic acid. There is a problem that only a large saturated fatty acid can be removed.

Representative Fatty Acids in Vegetable Oils Molecular Weight Palmitic acid (16: 0) stearic acid (18: 0) oleic acid (18: 1) linoleic acid (18: 2) 256.42 284.48 282.46 280.44

That is, only molecular distillation can remove only palmitic acid (palmitic acid, 16: 0), which is a saturated fatty acid contained in vegetable oil, among the fatty acids listed in Table 1, and stearic acid is Almost no removal. For example, safflower oil, which is commonly used as a raw material for the preparation of conjugated linoleic acid, contains about 5-7% of palmitic acid and 1-3% of stearic acid.

US Pat. No. 6,762,313 discloses an example in which safflower oil fatty acids are molecularly distilled to remove saturated fatty acids for use as a raw material of conjugated linoleic acid. Palmitic acid (16: 0) decreased significantly from 6.01% to 0.99%, while stearic acid (18: 0) increased from 2.80% to 3.10%. In addition, after removing saturated fatty acid through molecular distillation in US Pat. No. 7,067,684, the saturated fatty acid content of the synthesized conjugated linoleic acid is disclosed in Table 3c, where the palmitic acid (palmitic acid, 16: 0) is 1.3%. In contrast, stearic acid (18: 0) remains unremoved at 2.7%.

Therefore, the conventional molecular distillation method can effectively remove palmitic acid, but stearic acid has little disadvantage of removing. The conjugated linoleic acid content can only be increased by 3 to 5%, which is the amount of palmitic acid removed.

Another disadvantage of the process is that the fatty acid fatty acid is converted to methyl ester or ethyl ester and then subjected to molecular distillation process. Organic solvents such as methanol or ethanol must be used in the methyl ester or ethyl esterification process, and the catalyst is also used as sodium ethoxide, potassium ethoxide, and sodium methoxide. Or it should use a catalyst that can not be used as a food additive, such as potassium methoxide (potassium methoxide), there may be a problem in the human safety of the conjugated linoleic acid composition prepared according to the manufacturing method, conjugated linoleic acid composition applied to functional food As not preferred.

In addition, Korean Patent No. 10-0539357 discloses a method for preparing high content conjugated linoleic acid by ethanol-aqueous solution urea addition method and Korean Application No. 10-2000-0008927 by methanol-urea addition method.

The ethanol-aqueous solution urea addition method (secondary nucleation mechanism) disclosed in Korean Patent No. 10-0539357 is synthesized by conjugated linoleic acid, followed by addition of urea to the ethanol-aqueous solution to purify conjugated linoleic acid. It is a method of separating and purifying the inclusion compound of. The disadvantage of the method is that the content ratio of c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid in the isomer of the final product conjugated linoleic acid is difficult to produce 50:50. That is, since the reactivity of c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid to form a urea clathrate compound is different, the content of t10, c12 conjugated linoleic acid is particularly reduced.

     Republic of Korea Patent No. 10-0539357 does not give a clear content for each isomer, such as c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid to the results of the conjugated linoleic acid production, only reveals that the yield is 93.0%. In the preparation of conjugated linoleic acid according to the patented method, each isomer content is as follows, and the GC (gas chromatography) graph is shown in FIG. 3.

Conjugated linoleic acid (CLA) isomer content % c9, t11 conjugated linoleic acid (CLA) 38.49 t10, c12 conjugated linoleic acid (CLA) 32.32

That is, it can be seen that the content ratio of c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid is approximately 1.2: 1 when the conjugated linoleic acid is prepared according to the patent method. This is because c9, t11 conjugated linoleic acid is more easily contained in urea than t10, c12 conjugated linoleic acid. In the 7.0% conjugated linoleic acid composition, the remaining portion other than the yield of 93.0% disclosed in the patent, there is a problem that a considerable amount of t10, c12 conjugated linoleic acid remains.

According to many scientific papers on conjugated linoleic acid, it is reported that conjugated linoleic acid is most preferable in terms of functional and human safety when the content ratio of c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid is 50:50.

Therefore, when the conjugated linoleic acid is produced by the above patent method, it is difficult to produce a preferable high content of conjugated linoleic acid due to the content imbalance of the conjugated linoleic acid isomer.

On the other hand, the two-step conjugated linoleic acid-urea clathrate process has to be performed and the process of drying the urea clathrate compound for a long time has a disadvantage in that the process time is very long. The addition of nine times the amount of linoleic acid raises a huge productivity problem in terms of mass production of tens of tonnes of product. On the other hand, it can be seen that the manufacturing method also uses an organic solvent called ethanol to apply the urea addition method.

In addition, the methanol-urea addition method disclosed in the Republic of Korea Application No. 10-2000-0008927 is a raw material of vegetable oil (safflower oil or sunflower oil, etc.) containing a high concentration of methanol: urea: linoleic acid 3-4: 1.5-2.0: 1 The mixture mixed at the ratio was raised to 60-70 ° C. to completely dissolve it, and then cooled to adjust the final temperature to 20-30 ° C., and the obtained mixture was filtered to recover liquid phases and methanol was evaporated at this time. Provided is a method for producing conjugated linoleic acid of at least 99% purity linoleic acid prepared by removing urea and hexane from the crystals thus obtained by a high temperature salt forming isomerization method (according to AAOAC method).

The manufacturing method uses an organic solvent called methanol which is very harmful to the human body in order to apply the urea addition method, and it is applied to the functional food in terms of safety because it causes a process troublesome to synthesize conjugated linoleic acid after removing the methanol. It is not preferable as a method for producing a conjugated linoleic acid composition, which is very inefficient in terms of productivity.

In addition, Korean Patent No. 10-0256827 discloses a method for separating and purifying unsaturated fatty acids in a fish oil system containing hexane-urea-oleic acid as another method for producing a high purity unsaturated fatty acid by the urea addition method. The manufacturing method provides a method of increasing the activity of non-activated general urea by using a phase transition phenomenon of oleic acid. That is, when the oleic acid is included in the solid urea and then cooled to a low temperature of 4 ° C. or less, the oleic acid causes a phase transition phenomenon to cause cracks on the surface of the solid urea, thereby increasing the activity of the solid urea to separate unsaturated fatty acids. It is a method of purification. The main disadvantage of this method is that the reaction system must be cooled to 4 ° C or lower. That is, in order to cool to a low temperature, an organic solvent such as hexane must be used essentially, because a large amount of saturated fatty acids exist in fish oil or vegetable oil, and when cooled to 4 ° C. or lower without using an organic solvent, This is because it is almost impossible to carry out this method without using an organic solvent because the entire reaction system is hardened.

In addition, as the cracking phenomenon occurs on the surface of the solid urea, the unsaturated fatty acids to be separated, such as gamma-linolenic acid, DHA and EPA, are also included in the solid urea, which causes a huge problem in yield reduction according to the production process. In mass production, the huge reaction system has to be cooled down to 4 ° C or less, which greatly affects the equipment cost and processing time. Another problem that arises in mass production by the above method is that it is difficult to reach the target purity of the unsaturated fatty acid to the target purity in a single process by the above method, and the additional oleic acid must be continuously added when the repeated process is performed. There is this.

Therefore, the manufacturing method may be referred to as a manufacturing method which is not suitable for mass production, and in this method, an organic solvent called hexane should be used, and thus it is not preferable as a method for providing a conjugated linoleic acid and gamma-linolenic acid composition used as a health functional food. .

In addition, Korean Patent No. 10-0387941 discloses a partial crystallization method using an organic solvent as another method for producing high purity conjugated linoleic acid, which method methyl esterifies conjugated linoleic acid, Acetone) to prepare a high purity conjugated linoleic acid through a partial crystallization method according to the freezing point. The biggest drawback of the patent is that the partial crystallization process must be carried out at minus 68 ° C., which can cause fatal problems for process time and equipment in actual mass production. In addition, as described in the embodiments of the patent, the content ratio of c9, t11 conjugated linoleic acid and t10, c12 conjugated linoleic acid has a disadvantage that the content ratio varies greatly depending on the precipitate and the supernatant, and the manufacturing method is very harmful to the human body It can be seen that a solvent is used.

Therefore, high purity conjugated linoleic acid prepared according to the above production method is also undesirable as a conjugated linoleic acid composition applied to functional food.

In short, all of the above conventional manufacturing methods use an organic solvent, the composition ratio of the two isomers is not balanced about 50:50, and does not completely remove saturated fatty acids, so the conjugated linoleic acid composition applied to functional foods As not very desirable.

Conventional high-purity gamma-linolenic acid production method is also not different from the production method of the high-purity conjugated linoleic acid, there is no case that provides a method for producing without using an organic solvent.

Throughout this specification many patent documents are referenced and their citations are indicated. The disclosures of the cited patent documents are incorporated by reference herein in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly described.

The present inventors endeavored to develop a production method capable of mass-producing high-purity unsaturated fatty acids without using organic solvents harmful to human bodies, unlike conventional methods for producing high-purity unsaturated fatty acids. As a result, using only active organic-elements that maximize the reactivity by drying with a vacuum spray dryer without using an organic solvent, effectively removes saturated fatty acids, and maximizes the content of physiologically active ingredients. Increasing and confirming that mass production can be made inexpensively in a simpler and more efficient process has led to the present invention.

Accordingly, it is an object of the present invention to provide a process for producing highly pure unsaturated fatty acids.

      Another object of the present invention is to provide a method for preparing an urea by drying an aqueous urea solution in a vacuum spray dryer.

Other objects and advantages of the present invention will become apparent from the following detailed description, claims and drawings.

According to one aspect of the invention, the invention provides a process for the preparation of highly pure unsaturated fatty acids comprising the following steps:

(a) drying the aqueous urea solution with a vacuum spray dryer to prepare a preactivated urea;

(b) injecting the free fatty acid obtained by hydrolyzing the vegetable oil into the reactor;

(c) adding and mixing the preactivated urea prepared in step (a) into the reactor of step (b);

(d) filtering the mixture of step (c) to remove saturated fatty acids; And

(e) distilling and purifying the free fatty acid filtered in step (d).

The present inventors endeavored to develop a production method capable of mass-producing high-purity unsaturated fatty acids without using organic solvents harmful to human bodies, unlike conventional methods for producing high-purity unsaturated fatty acids. As a result, using only active organic-elements that maximize the reactivity by drying with a vacuum spray dryer without using an organic solvent, effectively removes saturated fatty acids, and maximizes the content of physiologically active ingredients. A method for producing a high purity unsaturated fatty acid which has been increased and can be mass produced inexpensively in a simpler and more efficient process has been developed.

The present invention relates to a process for producing highly pure unsaturated fatty acids. The unsaturated fatty acid produced by the present invention is an unsaturated fatty acid having 10 to 30 carbon atoms and 1 to 6 double bonds, preferably mystoleic acid, palmitoleic acid, and linoleic acid. , Conjugated linoleic acid, alpha-linolenic acid (α-linolenic acid), gamma-linolenic acid (γ-linolenic acid), oleic acid (oleic acid), DHA (docosahexaenoic acid) or EPA (eicosapentaenoic acid), more preferably linoleic acid (linoleic) acid, conjugated linoleic acid, gamma-linolenic acid, alpha-linolenic acid or oleic acid, most preferably linoleic acid, conjugated linoleic acid (conjugated linoleic acid) or gamma-linolenic acid.

Detailed description of the process of the present invention for producing a high purity unsaturated fatty acid is as follows:

(a) Preparation of Inactivating Element

The activated urea used in the present invention is prepared by stirring and dissolving urea in water to prepare an aqueous urea solution, and drying the urea solution using a vacuum spray dryer. The drying is preferably carried out under high temperature and reduced pressure conditions, the temperature is more preferably carried out at 50-150 ℃, most preferably at 80-100 ℃, the pressure is more preferably 10 ^-1 -10 ^-3 torr, most preferably at 10 ⁻² torr. By instant drying using a vacuum spray dryer under such high temperature and depressurization conditions, it is possible to maximize the reactivity of the urea by completely removing and recrystallizing the moisture remaining in the surface of the urea and the interior of the urea. The use of only active ingredients allows the removal of unsaturated fatty acids from free fatty acids without the use of organic solvents and wetting agents.

The activated urea produced by this recrystallization process is a fine urea powder, and the urea powder is kept sealed and kept at constant temperature and humidity in a sealed package.

(b) free fatty acid obtained by hydrolysis of vegetable fats and oils into the reactor;

The free fatty acid used in the present invention is obtained by hydrolysis of vegetable oils extracted and purified from vegetable seeds, preferably liquid free fatty acids. The vegetable oil is preferably safflower oil, borage oil, sunflower oil, soybean oil, jade oil, evening primrose seed oil or black currant oil, depending on the type of unsaturated fatty acid to be prepared, the vegetable oil is hydrolyzed. For example, when producing high purity linoleic acid, the vegetable oil is safflower oil, sunflower oil, soybean oil or jade oil, more preferably safflower oil, and when producing high purity gamma-linolenic acid, the vegetable oil is borage oil, evening primrose oil or blackcurrant. Oil, more preferably borage oil.

In general, when oil is separated from plants, it is obtained in the form of triglycerides. Such triglycerides can be hydrolyzed to obtain free fatty acids. Hydrolysis is intended to liberate fatty acids from vegetable fats and oils in the form of triglycerides, which is possible by enzymatic or chemical treatment. The chemical treatment is preferably an acid or base aqueous solution, more preferably hydrochloric acid or sodium hydroxide aqueous solution.

Hydrolysis of triglycerides can be carried out through various methods. For example, water and triglycerides can be reacted and hydrolyzed under conditions of high pressure and high temperature (eg, 700 psi and 250 ° C.). In addition, free fatty acids can be obtained from triglycerides via the Twitchell process. Specifically, triglycerides can be mixed with water and petroleum-alkyl benzene sulfonic acid and heated for 36-48 hours with open steam to hydrolyze the triglycerides. The Journal of The American Oil Chemists' Society 39: 1-6 (1962) discloses a hydrolysis method of triglycerides, which hydrolyzes triglycerides with acetic acid in the presence of a strong acid catalyst. US Pat. No. 4218386 discloses a process for reacting triglycerides with water in the presence of a substituted acid catalyst to obtain free fatty acids.

In addition, lipase enzymes from various sources can be used to hydrolyze triglycerides. For example, Rhizopus arrhizus lipase (U.S. Pat. No. 3,759,793) and Pseudomonas fluorescens lipase (Chimica Chimica Acta, 81 (1977) 125: 130) can be used to enzymatically hydrolyze triglycerides.

The free fatty acid produced by hydrolysis is added to the reactor.

(c) mixing of active ingredients and free fatty acids

Subsequently, only the preactivated urea powder is added to the reactor in which the liquid free fatty acid is added and stirred to allow the preactivated urea to selectively contain the saturated fatty acid. In removing saturated fatty acid from glass paper dispersion, the present invention does not use an organic solvent and a humectant by preparing and using urea maximized reactivity by using a vacuum spray dryer. On the other hand, in the case of urea produced through a general drying process such as hot air drying and oven drying after recrystallization of the conventional urea, drying takes a long time and due to moisture remaining on the surface of the urea and the interior of the urea inside the urea The surface of the urea is recrystallized to decrease its activity, thereby reducing its reactivity with saturated fatty acids, thereby making it impossible to effectively remove saturated fatty acids.

Due to this problem, we need to use an organic solvent such as hexane, ethanol and methanol, or a wetting agent such as a polar solvent to lower the viscosity of the lipid or increase the activity of the urea to induce the reaction of the urea and the lipid.

(d) Filtration of the mixture and removal of saturated fatty acids

Next, urea sludge and saturated fatty acid are separated. Preferably, urea sludge and saturated fatty acid are separated using a filter press. After re-inserting the separated liquid into the reactor, it is preferable to further carry out an iterative process of adding the same amount of group active-urea, more preferably twice in the case of linoleic acid production, to prepare gamma-linoleic acid. In the case of 4 additional repeat process.

Saturated fatty acids removed from free fatty acids by preactivated urea are preferably palmitic acid and stearic acid, and other unnecessary lipid components are also removed.

According to a preferred embodiment of the invention, the content of saturated fatty acids in the product of step (d) prepared by the removal of saturated fatty acids is 1.0% or less, more preferably the total content of palmitic acid and stearic acid is 1.0% or less Becomes

(e) distillation purification of filtered free fatty acids

The filtered free fatty acid is distilled and purified to obtain high purity unsaturated fatty acid. Distillation of the free fatty acids can be carried out according to conventional methods known in the art. Typically, the free fatty acid is distilled off under reduced pressure and high temperature conditions. For example, free fatty acids may be distilled by short path distillation or distillation using a thin film evaporator. Preferably, the distillation of the free fatty acid is carried out using a thin film still. In the case of distillation using a thin film distillator, preferably the pressure is 10 ^-1 -10 ^-3 torr, more preferably at 10 ^-2 torr, the temperature is 170-190 ° C.

Finally, the free fatty acid obtained by distillation and purification of the filtered free fatty acid is methyl esterified, and then analyzed by gas chromatography. A high-purity unsaturated fatty acid such as high purity in which almost or completely saturated fatty acids such as palmitic acid and stearic acid is removed It can be confirmed that the linoleic acid (linoleic acid) or gamma-linolenic acid was prepared.

According to a preferred embodiment of the present invention, the high purity linoleic acid prepared by the present invention has a content of at least 90%, more preferably at least 95% and most preferably at least 97% in the result of step (e).

According to another preferred embodiment of the present invention, the high purity gamma-linolenic acid produced by the present invention has a content of at least 60% in the result of step (e).

According to another preferred embodiment of the present invention, it is possible to prepare high purity conjugated linoleic acid, including the following additional steps.

(f) Alkali Reaction of Linoleic Acid

The free fatty acid prepared in step (e) is subjected to an alkali reaction, preferably a saponification reaction.

According to a preferred embodiment of the present invention, the alkali reaction is carried out using a base dissolved in glycol or glycerol.

According to another preferred embodiment of the present invention, the glycol is ethylene glycol, diethylene glycol, triethylene glycol, methylene glycol, dimethylene glycol, trimethylene glycol, propylene glycol, dipropylene glycol, butylene glycol or mixtures thereof, More preferably, it is ethylene glycol or propylene glycol, most preferably propylene glycol.

The base dissolved in the glycol is preferably sodium hydroxide or potassium hydroxide, more preferably sodium hydroxide.

The alkali reaction is preferably carried out at 120-250 ° C, more preferably at 170-200 ° C. The alkali reaction is carried out at such a high temperature to sufficiently dissolve the base in glycol by using a high boiling point of glycol.

(g) Preparation of high purity conjugated linoleic acid

The acid solution is added and stirred to the result of step (f). The addition of the acid solution is for converting the salt form product into conjugated linoleic acid. As the acid to be used, any conventional acid may be used. For example, hydrochloric acid, sulfuric acid, acetic acid, carboxylic acid, phosphoric acid, and the like may be used. Most preferably, the acid solution is an aqueous hydrochloric acid solution.

Through this additional process it is possible to produce a high purity conjugated linoleic acid, the high purity conjugated linoleic acid is preferably at least 90%, more preferably at least 95%, most preferably at least 97%.

The conjugated linoleic acid produced by the present invention is cis-9, trans-11 C18: 2, trans-10, cis-12 C18: 2, cis-9, cis-11 C18: 2, cis-10, cis-12 C18 : 2 and trans-9, trans-11 C18: 2 + trans-10, trans-12 C18: 2 isomers are conjugated, preferably cis-9, trans-11 C18: 2 and total conjugated linoleic acid The content of trans-10, cis-12 C18: 2 is 92-98%, more preferably 94-97%, most preferably 95-96%.

According to a preferred embodiment of the present invention, the content ratio of the isomers cis-9, trans-11 C18: 2 and trans-10, cis-12 C18: 2 is 0.95-1: 1, more preferably 0.97-0.99 : 1, most preferably 0.98-0.99: 1.

According to another aspect of the present invention, there is provided a method of making an urea by drying an aqueous urea solution with a vacuum spray dryer.

Since the method of the present invention is a method for producing a preactivation element for producing the high purity unsaturated fatty acid of the present invention described above, the common content between the two is omitted, in order to avoid excessive complexity of the specification according to the repeated description. do.

According to a preferred embodiment of the invention, the activating element has a use for the separation of saturated fatty acids in vegetable oils and fats.

According to a preferred embodiment of the present invention, the drying is preferred to dry the aqueous urea solution under high temperature and reduced pressure conditions, the temperature is more preferably 50-150 ℃, most preferably at 80-100 ℃, the pressure is more It is preferably carried out by drying in a vacuum spray dryer at 10 ^-1 -10 ^-3 torr, most preferably at 10 ^-2 torr.

The features and advantages of the present invention are summarized as follows:

(Iii) The present invention provides a process for producing unsaturated fatty acids of high purity.

(Ii) In order to increase the activity of urea for selective inclusion and removal of saturated fatty acids, instead of using organic solvents harmful to the existing human body, the drying reactivity is maximized using a vacuum spray dryer under high temperature and reduced pressure conditions. Use activated activation elements.

(Iii) Saturated fatty acids can be effectively removed from the free fatty acids by the activating element maximized reactivity, thereby producing high purity linoleic acid and conjugated linoleic acid having a content of 90% or more, or high purity gamma-linolenic acid of 60% or more.

(Iii) In particular, the content of specific isomers conjugated for the physiological activity of conjugated linoleic acid is important, but the conjugated linoleic acid prepared by the present invention exhibits cis-9, trans-11 C18: 2 and trans-10, Since the content of two isomers of cis-12 C18: 2 is 95-96% and the content ratio of the two isomers is 0.95-1: 1, the present invention can prepare conjugated linoleic acid in which the functionality and safety are maximized.

(Iii) In addition, the present invention can mass-produce high-purity unsaturated fatty acids at low cost in a simpler and more efficient process.

As described in detail above, the present invention provides a method for producing unsaturated fatty acids of high purity. The present invention, in order to increase the activity of the urea for the selective inclusion and removal of saturated fatty acids, instead of using an organic solvent harmful to the existing human body, a device that maximizes dry reactivity using a vacuum spray dryer under high temperature and reduced pressure conditions Use the active element. Thus, it is possible to effectively remove the saturated fatty acid from the free fatty acid, it is possible to produce a high purity unsaturated fatty acid of maximized content.

In particular, the content of specific isomers conjugated for the physiological activity of conjugated linoleic acid is important, the conjugated linoleic acid prepared by the present invention is cis-9, trans-11 C18: 2 and trans-10, cis- By maximizing the content of the two isomers of 12 C18: 2 and keeping the content ratio of the two isomers constant, the present invention can prepare conjugated linoleic acid with maximized functionality and safety. In addition, the present invention can mass-produce high-purity unsaturated fatty acids at low cost in a simpler and more efficient process.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples in accordance with the gist of the present invention to those skilled in the art. Will be self explanatory.

Example  One

2 kg of urea was dissolved in 3 L of water at 100 ° C. The urea aqueous solution was momentarily dried using a vacuum spray dryer (DR101, B & D Engineering Co., LTD.) At 150 ° C. and 10 ⁻² torr. The elements harvested in this process were sealed and packaged and kept at constant temperature and humidity.

Example  2

47,000 g of free fatty acid obtained by hydrolyzing 50,000 g of safflower oil were added to a 300 L reactor, and 15,000 g of the active active-urea powder prepared in Example 1 was added to safflower oil free fatty acid at room temperature. Stirred for 1 hour. Then, the urea sludge and the saturated fatty acid were separated using a filter press (IWF-42, Ilwoong Industry), and the remaining liquid was re-injected into the reactor, and then the same amount of group activity- Two additional steps of adding urea were carried out. Finally, the filtered free fatty acid was distilled off. Distillation purification of the free fatty acid was carried out using a thin film distillator, pressure was 10 ⁻² torr and temperature was 190 ° C.

0.3 g sample of distilled and purified free fatty acid (24,500 g) was methyl esterified and analyzed by gas chromatography (Agilent 6890N). Palmitic acid and stearic acid were completely removed and linoleic acid was the main component of safflower oil. Was 98.9%.

Example  3

After dissolving 100 g of sodium hydroxide in 1 kg of propylene glycol at 60 ° C, the temperature was gradually raised to 180 ° C. 400 g of 98.9% of linoleic acid obtained in Example 2 were slowly added to the solution, followed by stirring at 180 ° C. for 2 hours 30 minutes. Then, after slowly cooling to 80 ° C, 500 g of 18% aqueous hydrochloric acid solution was added thereto and stirred. Then, the stirring was stopped and the phase separated to take the supernatant. As a result of analyzing the supernatant by gas chromatography (Agilent 6890N), c9, t11 C18: 2 (46.7%), t10, c12 C18: 2 (47.5%), c9, c11 C18: 2 (1.3%) as shown in FIG. 395 g of c10, c12 C18: 2 (1.2%), t9, t11 C18: 2 + t10, t12 C18: 2 (1.5%) and total conjugated linoleic acid (98.2%) were obtained.

Example  4

23,000 g of free fatty acid obtained by hydrolysis of 25,000 g of Borage oil were added to a 300 L reactor, and 6,900 g of active-element urea prepared in Example 1 was added to Borage oil free fatty acid, and then at room temperature. Stirred for 1 hour. Next, the urea sludge and the saturated fatty acid were separated using a filter press, and the separated solution was re-injected into the reactor, and then the same process was repeated four times. It was further carried out. Finally, the filtered free fatty acid was distilled and purified, 0.3 g of the free fatty acid (13,400 g) was taken, methyl esterified, and analyzed by gas chromatography (Agilent 6890N). 2, the gamma-linolenic acid content in the free fatty acid was 61.85%.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that such a specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

1 is a graph of GC (Gas Chromatography) analysis of conjugated linolenic acid having a purity of 90% or more without using an organic solvent according to Example 3 of the present invention. CLA stands for conjugated linoleic acid. Kinds and contents of isomers of conjugated linoleic acid prepared according to the present invention are c9, t11 C18: 2 (46.7%), t10, c12 C18: 2 (47.5%), c9, c11 C18: 2 (1.3%), c10 , c12 C18: 2 (1.2%) and t9, t11 C18: 2 + t10, t12 C18: 2 (1.4%), with a total conjugated linoleic acid content of 98.2%.

2 is a graph of GC analysis of gamma-linolenic acid having a purity of 60% or more without using an organic solvent according to Example 4 of the present invention. The content of gamma-linolenic acid produced by the present invention is 61.85%.

3 is a graph of GC analysis of conjugated linoleic acid prepared by the ethanol aqueous solution urea addition method of Korean Patent No. 0939357. CLA stands for conjugated linoleic acid. When prepared according to the present invention, saturated fatty acid, palmitic acid (7.6%) and stearic acid (3.2%) are present, and the type and content of isomers of conjugated linoleic acid are c9, t11 C18: 2 (38.5%), t10, c12 C18: 2 (32.3%), c9, c11 C18: 2 + c10, c12 C18: 2 (2.8%) and t9, t11 C18: 2 + t10, t12 C18: 2 (1.0%), total airspace The content of linoleic acid is 73.6%.

Figure 4 is a process chart showing a method for producing unsaturated fatty acid from vegetable oil according to the present invention in high purity. CLA stands for conjugated linoleic acid.

Claims (17)

A process for preparing a high purity unsaturated fatty acid comprising the following steps: (a) drying the aqueous urea solution with a vacuum spray dryer to prepare a preactivated urea; (b) injecting the free fatty acid obtained by hydrolyzing the vegetable oil into the reactor; (c) adding and mixing the preactivated urea prepared in step (a) into the reactor of step (b); (d) filtering the mixture of step (c) to remove saturated fatty acids; And (e) distilling and purifying the free fatty acid filtered in step (d). The method of claim 1 wherein the unsaturated fatty acid is linoleic acid or gamma linolenic acid. The method of claim 1, wherein the preactivating element is prepared by drying an aqueous urea solution in a vacuum spray dryer at 50-150 ° C and 10 ^-1 -10 ^-3 torr high temperature and reduced pressure conditions. The method of claim 1, wherein the vegetable oil is selected from the group consisting of safflower oil, borage oil, sunflower oil, soybean oil, jade oil, evening primrose seed oil and blackcurrant oil. The method of claim 1, wherein the saturated fatty acid removed in step (d) is palmitic acid and stearic acid. The method of claim 1 wherein the product of step (d) comprises less than 1.0% saturated fatty acids. The method of claim 1, wherein the method comprises the steps of: (f) alkali reaction of the free fatty acid obtained in step (e); And (g) adding and stirring the acid solution to the product of step (f) to produce conjugated linoleic acid. 8. The process of claim 7, wherein the alkali reaction of step (f) is carried out using a base dissolved in glycol or glycerol. 8. The process of claim 7, wherein the alkali reaction is carried out at 120-250 ° C. The method of claim 2 wherein the content of linoleic acid in the product of step (e) is at least 90%. The method of claim 2, wherein the content of gamma-linolenic acid in the result of step (e) is at least 60%. 8. The method of claim 7, wherein the content of conjugated linoleic acid in the product of step (g) is at least 90%. 8. The method of claim 7, wherein said conjugated linoleic acid has a content of isomers of cis-9, trans-11 C18: 2 and trans-10, cis-12 C18: 2 of 95-96%. The method of claim 13, wherein the content ratio of the isomers cis-9, trans-11 C18: 2 and trans-10, cis-12 C18: 2 is 0.95-1: 1. A method of making an urea by drying an aqueous urea solution in a vacuum spray dryer. 16. The method of claim 15, wherein the activating element has a use for the separation of saturated fatty acids in vegetable oils and fats. 16. The method of claim 15, wherein the drying is performed by drying an aqueous urea solution in a vacuum spray dryer at 50-150 ° C and 10 ^-1 -10 ^-3 torr high temperature and reduced pressure conditions.

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