KR20170044852A - Purification and concentration method of omega-7 unsaturated fatty acids - Google Patents
Purification and concentration method of omega-7 unsaturated fatty acids Download PDFInfo
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- KR20170044852A KR20170044852A KR1020150144471A KR20150144471A KR20170044852A KR 20170044852 A KR20170044852 A KR 20170044852A KR 1020150144471 A KR1020150144471 A KR 1020150144471A KR 20150144471 A KR20150144471 A KR 20150144471A KR 20170044852 A KR20170044852 A KR 20170044852A
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- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
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Abstract
The present invention relates to a process for purifying omega-7 unsaturated fatty acids, and more particularly to a process for concentrating or purifying omega-7 fatty acid-based unsaturated fatty acids derived from natural fish oil in high purity.
Description
The present invention relates to a process for purifying omega-7 unsaturated fatty acids, and more particularly to a process for concentrating or purifying omega-7 fatty acid-based unsaturated fatty acids derived from natural fish oil in high purity.
Unsaturated fatty acid refers to a fatty acid having one or more double bonds in its molecular structure. It lowers cholesterol and has proven its efficacy in the prevention and treatment of circulatory diseases such as arteriosclerosis. In recent years, essential amino acids, essential vitamins and other essential fatty acids The significance of this issue is recognized as much as possible.
These are mainly linoleic acid or linoleic acid contained in seed oil or nuts such as safflower seed oil, sunflower seed oil, corn oil and perilla oil, alpha linolenic acid contained in flax seed oil or perilla seed oil, gamma linolenic acid contained in evening primrose oil, and saury, (EPA), docosahexaenoic acid (DHA) and the like, which are mainly contained in fresh fish such as sardines, mackerel and tuna, and arachidonic acid which is obtained directly from a microorganism or a microalga culture do.
These fatty acids are typical unsaturated fatty acids containing double bonds. Recently, they have been widely used from health functional nutraceutical food materials to raw material medicinal materials. They have started to use Nordic countries such as Sweden and Denmark, , And it is widely recognized as one of the foods that improve the quality of life (QOL).
Therefore, a variety of purification and concentration methods have been studied for regular and large-scale consumption of unsaturated fatty acids extracted from fish as pharmaceutical ingredients or food ingredients.
Korean Patent Publication No. 2012-0018219 (Patent Document 1) discloses a method for obtaining a concentrate of eicosapentaenoic acid and docosahexaenoic acid ester from crude or refined fish oil.
Recently, in addition to these omega-3 or DHA unsaturated fatty acids, the remarkable efficacy of omega-7 fatty acids has become known. Omega-7 fatty acid (palmitoleic acid; PLA) is a monounsaturated fatty acid having a double bond at the 7th carbon at the chain end. It has excellent effects on cardiovascular disease, gastrointestinal health, skin, hair, nail protection and weight reduction. Clinical results.
These omega-7 fatty acids are mainly contained in plants such as macadamia and seedy buckwheat, and fish such as saury, sardines, anchovies, sardines, mackerel and tuna.
Currently, the commercialized omega-7 fatty acids are mainly extracted from the Cubpton Barley, but it is a plant that lives only in the Tibetan Himalayan alpine region, which is 12,000 feet above sea level. It does not supply raw materials smoothly and contains phospholipids, Tocopherol, pigments, and viscous substances, which may cause pigmentation, fuming, or bubbling of the oil in the process during the processing.
Therefore, in order to solve such a problem and to obtain an omega-7 fatty acid having an increased content of active ingredients while being industrially easily applied, studies have been conducted to obtain omega-7 fatty acids in natural fish oil. However, natural fish oil contains 14 to 22 different fatty acids, and these fatty acids are easily oxidized in the air to form peroxides or to polymerize easily. In addition, there is a possibility that a malodor may occur due to a substance produced by oxidation and decomposition of an unsaturated fatty acid contained in natural fish oil.
Therefore, there is a need for a separate pretreatment method and a special purification process for selectively separating and concentrating these omega-7 fatty acids from fish oil.
In order to solve the above problems, it is an object of the present invention to provide a process for purifying omega-7 unsaturated fatty acids selectively in natural fish oil.
It is another object of the present invention to provide a purification process capable of improving productivity and obtaining a concentrated product of high concentration by performing a recrystallization process using an element after the distillation step.
It is also an object of the present invention to provide purified omega-7 unsaturated fatty acids using the above-described purification process.
To achieve the above object, the present invention provides a method for producing a fatty acid ester, comprising the steps of: a) preparing a fatty acid ester by ethanolysis of natural fish oil and ethanol in the presence of a base catalyst, b) distilling the fatty acid ester to obtain a concentrated fatty acid ester C) isolating and purifying the concentrated omega-7 fatty acid ester through a recrystallization process using urea, and d) separating the omega-7 fatty acid ester by secondary chromatography 7-unsaturated fatty acid including a step of purifying the omega-7 unsaturated fatty acid.
According to an embodiment of the present invention, the purifying step may further include a step of saponifying the natural fish oil before the step a), and pretreating the fatty acid to less than 1 wt%.
According to an embodiment of the present invention, the step a) may be carried out at 60 to 80 ° C for 1 to 4 hours, and 50 to 300 equivalent% of ethanol may be added to the natural fish oil equivalent.
According to an embodiment of the present invention, the step b) may be carried out at a temperature of from 100 to 200 ° C and from 0.001 to 20 mbar, and the step b) comprises: b-1) (ii) subjecting the first concentrated fatty acid esterified product to fractional distillation to prepare a second concentrated fatty acid esterified product, and (ii) subjecting the first concentrated fatty acid esterified product to distillation to obtain a first concentrated fatty acid esterified product can do.
According to an embodiment of the present invention, the b) may be a thin film molecular distillation or a continuous distillation method, and the continuous distillation may be distilled at a reflux ratio of 1 to 10 using a 20 to 40-stage distillation column.
According to an embodiment of the present invention, the step c) comprises mixing 150 to 300 parts by weight of the urea and 600 to 800 parts by weight of the solvent with respect to 100 parts by weight of the omega-7 fatty acid at a temperature of 50 to 70 캜, So that urea crystals can be precipitated.
According to an embodiment of the present invention, the omega-7 fatty acid obtained in the step c) may be mixed with menhaden oil, and the recrystallization process using the element of the step c) may be repeated.
According to one embodiment of the present invention, the step d) uses column chromatography, and the column chromatography uses high performance liquid chromatography (HPLC) and C18-ODS (Octa Desyl Silicate) columns And then subjected to secondary purification.
According to one embodiment of the present invention, the omega-7 unsaturated fatty acid that has undergone the purification process may be palmitoleic acid at a concentration of 90 wt% or more.
In order to achieve the above object, the present invention provides an omega-7 unsaturated fatty acid having a palmitoleic acid concentration of 90% by weight or more, a saturated fatty acid content of 0.1% by weight or less, 7 < / RTI > unsaturated fatty acids.
The process for purifying omega-7 unsaturated fatty acids of the present invention has an advantage of effectively concentrating omega-7 unsaturated fatty acids by introducing a stepwise distillation process by preliminary distillation and fractional distillation. In addition, there is an advantage that a high purity omega-7 unsaturated fatty acid can be obtained by effectively separating saturated fatty acids through a recrystallization process using an element.
In addition, the present invention is able to concentrate the omega-7 unsaturated fatty acid concentration to 90% or more by secondary separation and purification through the column chromatography of the firstly separated and purified fatty acid esterified product through the recrystallization process, There is an advantage in production.
FIG. 1 is a flowchart showing a purification process of omega-7 unsaturated fatty acids according to an embodiment of the present invention.
Hereinafter, preferred embodiments and methods for measuring the properties of the omega-7 unsaturated fatty acid purification process will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
Hereinafter, one embodiment of the present invention will be described in more detail.
FIG. 1 is a flow chart of a process for purifying omega-7 unsaturated fatty acids according to an embodiment of the present invention. 1, the process for purifying omega-7 fatty acids according to the present invention comprises the steps of: ethanolysis step (S10), distillation step (S20), first purification step (S30) and second purification step (S40) Lt; / RTI >
More specifically, the process for purifying omega-7 fatty acids according to the present invention comprises an ethanolysis step (S10), a preliminary distillation step (S21), a fractional distillation step (S22), a first purification step (S30) Step S40 may be performed.
The purification process according to one embodiment of the present invention may further include a) a pretreatment step prior to the ethanolysis step S10. The pretreatment step is a step of removing the fatty acid contained in the natural fish oil and saponifying the fatty acid so that the content of the fatty acid is less than 1% by weight. More specifically, sodium hydroxide (NaOH) is added to natural fish oil to saponify and the resulting fatty acid salt is washed with pure water and removed. At this time, since the fatty acid salt is dissolved in the pure water, the water layer may be separated from the oil layer and the water layer may be removed and the washing process may be repeated several times. At the end of the wash, the oil layer may be dehydrated under reduced pressure vacuum to remove residual moisture, but is not limited thereto.
A) ethanolysis step (S10) according to an embodiment of the present invention proceeds with trans esterification to convert natural fish oil in the form of triglyceride into fatty acid ester having low boiling point May be carried out by reacting ethanol with natural fish oil in the presence of a base catalyst. By performing the ethanolysis step, the triglycerides can be decomposed to produce three fatty acid esters and one glycerine.
The base catalysts include, but are not limited so long as the known become apparent to those skilled in the art, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium methoxide (NaOCH 3), PO dasyum methoxide (KOCH 3), Sodium ethoxide (NaOCH 2 CH 3 ) and potassium ethoxide (KOCH 2 CH 3 ). More preferably, sodium hydroxide (NaOH) may be selected, but is not limited thereto.
The step (S10) of ethanolysis according to one embodiment of the present invention may be carried out under conditions well known in the art. For example, the reaction may be conducted at 60 to 80 ° C for 1 to 10 hours, but is not limited thereto. When the ethanolysis reaction temperature is less than 60 ° C or the reaction time is less than 1 hour, the ethanolysis reaction is insufficient and the conversion rate may decrease. When the reaction temperature exceeds 80 ° C or the reaction time exceeds 10 hours There is a possibility that impurities such as cyclic fatty acid monomers or oligomers are produced by pyrolysis at high temperatures.
According to one embodiment of the present invention, ethanol may be added in an amount of 50 to 300 equivalent%, more preferably 150 to 300 equivalent%, based on the natural fish oil equivalent.
The reaction conditions and the ethanol content described above are effective to enhance the conversion of triglyceride to fatty acid ester.
For example, when the proper amount of natural fish oil, ethanol and sodium hydroxide (NaOH) is added to the reactor and the reaction is carried out at 60 to 80 ° C for 2 to 4 hours, the conversion rate of the fatty acid esterified product may be 99.0% or more. After the completion of the reaction, excess ethanol is recovered by distillation under reduced pressure, and the remaining product is stuck at 60 to 80 ° C, whereby the fatty acid ester and glycerin are separated due to the difference in specific gravity. Glycerin, which has a high specific gravity, is separated into lower layer portions, and when it is removed, a fatty acid ester can be obtained. In order to remove glycerin, fatty acid salts, and other water-soluble impurities remaining in the obtained fatty acid ester, washing with water may be repeated, and when water is removed under reduced pressure, fatty acid esters may be obtained, but the present invention is not limited thereto.
The following step b) is a step of distilling the fatty acid ester obtained in step a) into a distilled step (S20) to prepare a concentrated fatty acid esterified product. More specifically, by conducting fractional distillation (S22) through preliminary distillation (S21), it is possible to obtain a highly concentrated purified fatty acid esterified product, and it is possible to selectively obtain palmitoleic acid having 16 carbon atoms.
(B-1) preliminary distillation step (S21) is a step of preliminarily distilling the fatty acid ester prepared in step (a) with a short path distillation (SPD) apparatus to prepare a first concentrated fatty acid esterified product.
At this time, the reaction conditions may be carried out under conditions known to those skilled in the art. For example, the reaction temperature can be performed at 100 to 200 ° C, and the reaction pressure can be performed at 0.001 to 20 mbar, but is not limited thereto.
When the reaction conditions are in the above range, the yield of the omega-7 fatty acid ester can be improved, and generation of impurities such as heat-transforming substances can be suppressed.
The preliminary distillation step (S21) according to an embodiment of the present invention may be performed by using a thin-film molecular distillation apparatus or a continuous distillation apparatus with a short path distillation (SPD), but the present invention is not limited thereto.
The short distillation apparatus can evaporate and concentrate a substance having a low thermal stability in a short time in a short period of time because the interval between the evaporation region and the condensation region is short, and by performing at a relatively low temperature of less than 200 ° C, .
The present invention is advantageous in that the surface area per unit volume is remarkably increased by the use of a single distillation (SPD) apparatus and rapid evaporation is possible, and destruction or damage of fatty acids sensitive to oxidation and oxidation is minimized.
The thin-film molecular distillation apparatus can condense and recover omega-7 fatty acid, which is a low-boiling component, and concentrate the omega-7 fatty acid component containing about 9 wt% of the initial natural fish oil to about 15 wt% .
In addition, when the continuous distillation apparatus is utilized, the number of distillation columns is not limited, but may be 20 to 40 stages. When this is used, there is an advantage that the omega-7 fatty acid component containing about 9% by weight of the initial natural fish oil can be concentrated to about 20% by weight.
Next, as described above, the secondary condensed fatty acid ester product can be obtained through the b-2) fraction distillation step (S22) of the primary condensed fatty acid ester through the preliminary distillation step (S21).
Unlike the continuous process performed at the time of the preliminary distillation, the fractional distillation step (S22) can be separated by the distillation column and reflux ratio of 20 or more stages and batchwise by the fatty acid fraction. Depending on the reflux ratio, low fatty acids having a carbon number of 15 or less can be sequentially removed and omega-7 fatty acids having 16 carbon atoms can be concentrated and recovered.
The reaction pressure of the fractional distillation may be 1 to 20 mbar, and the reaction temperature may be 100 to 200 ° C, but is not limited thereto. When the reaction is carried out under the above reaction conditions, the fractional distillation efficiency is increased, and generation of heat deformations can be prevented, which is effective.
More specifically, after the column is stabilized, the omega-7 fatty acid can be distilled by changing the reflux ratio to 8 to 10 after removing the low-boiling fraction at a reflux ratio of 1 to 3. Omega-7 fatty acid esters having a carbon number of 16 can be obtained when the temperature at the upper part of the column is 170 to 190 ° C. When the temperature is above 170 ° C, the distillation can be stopped and a high boiling fraction having a carbon number of 17 or higher can be recovered as a residue. More preferably, the temperature of the upper portion of the column may be in the range of 180 to 185 ° C. In this temperature range, the selectivity of the omega-7 fatty acid ester having 16 carbon atoms can be remarkably improved and the formation of other impurities can be prevented effective.
More specifically, although the number of distillation columns is not limited, it is preferably 20 to 40 stages, more preferably 30 to 40 stages, and it is effective to remarkably improve the selectivity of omega-7 fatty acid esters having 16 carbon atoms.
Next, in step c) according to an embodiment of the present invention, the concentrated fatty acid esterified product obtained in the step b) is subjected to a recrystallization process using the urea to convert the omega-7 fatty acid ester into 1 This is a step for car separation and purification.
The first separation and purification step (S30) is a step for separating the saturated fatty acid and the unsaturated fatty acid remaining in the concentrated omega-7 fatty acid. When the urea and the fatty acid ester are dissolved in methanol and the urea is crystallized, The saturated fatty acid can be separated and purified by capturing the saturated fatty acid.
The primary separation and purification step (S30) may include crystallizing the element by mixing 150 to 300 parts by weight of the urea and 600 to 800 parts by weight of the solvent with respect to 100 parts by weight of the omega-7 fatty acid ester concentrated in the step b) But is not limited thereto.
More specifically, the omega-7 fatty acid ester, urea and methanol concentrated in the reactor are charged and the temperature is raised to 50 to 70 캜. When the temperature of the reactant is about 60 ° C or higher, all of the urea is dissolved in methanol. After confirming that all of the urea are dissolved, the reaction is gradually cooled to 10-20 ° C. When the urea crystallization is completed, the reaction product is filtered and separated into urea crystals and a methanol solution. Then, a salt aqueous solution such as sodium chloride (NaCl) or potassium chloride (KCl) is added to the methanol solution to form a methanol mixture layer and an omega-7 fatty acid ester layer Separate. When the omega-7 fatty acid ester layer is washed with water to remove impurities and degassed, a high-purity omega-7 fatty acid ester can be obtained.
According to an embodiment of the present invention, the omega-7 fatty acid ester obtained in the step c) may be mixed with menhaden oil, and the recrystallization process using the elements of the step c) may be repeated.
The menhaden oil can be added to effectively increase the content of omega-7 fatty acid ester and to reduce the manufacturing cost by using natural herbal-derived natural fish oil having the composition shown in Table 1 below.
[Table 1]
Next, in step d) according to an embodiment of the present invention, the omega-7 fatty acid ester obtained in the step c) is subjected to second separation and purification through column chromatography to a second separation and purification step (S40) . Through the second separation and purification step, an omega-7 unsaturated fatty acid having a palmitoleic acid concentration of 90 wt% or more can be obtained.
The column chromatography may be carried out using liquid chromatography (LC), high performance liquid chromatography (HPLC), True Moving Bed (TMB) or Simulated Moving Bed ; SMB) method can be used, and more preferably high performance liquid chromatography (HPLC) can be used.
When HPLC is used in the second separation and purification step, C18-ODS (Octa Desyl Silicate) can be used as a stationary phase, and the mobile phase can be separated and purified using methanol, but the present invention is not limited thereto. In the case of the second separation and purification using HPLC under the above-mentioned conditions, it is possible to produce a product having a short separation time and high concentration of concentrated omega-7 unsaturated fatty acid at 90% or more.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments of the omega-7 unsaturated fatty acid purification process of the present invention and a method for measuring a property thereof will be described in detail.
Property measurement
1. GC (Gas Chromatography) Analysis
The composition and concentration of the omega-7 fatty acid used in the present invention was determined by using Agilent's 7890A gas chromatography system. The column used was an omega-wax quartz glass tube (manufactured by supelco) fused silica capillary column (30m × 0.32mm × 0.25μm), and FID was used as the detector. The temperature of the injector was increased to 250 ° C, the temperature of the detector was increased to 270 ° C and the temperature of the initial oven was increased to 170 ° C to 225 ° C (1 ° C / min). Carrier gas was helium psi) was used.
[Example 1]
Natural fish oil pretreatment step
10.6 g of NaOH and 200 g of purified water were added to 1 kg of enchobio oil having an acid value (AV) of 7.5 mgKOH / g, and the mixture was heated to 60 DEG C and stirred for 1 hour. After completion of the reaction, the oil layer and the water layer are separated, and the water layer containing the fatty acid salt is removed. 200 g of purified water was further added, the temperature was raised to 60 ° C, and the mixture was further stirred for 30 minutes, and then the water layer was removed twice. After the completion of water washing, dehydration is performed under reduced pressure vacuum to remove water remaining in the oil layer. The pretreated natural fish oil has an acid value (AV) of 0.5 mgKOH / g or less and water content of 0.1% by weight or less.
Ethanolysis of pretreated natural fish oil
1 kg of the pretreated natural fish oil, 483 g (10.5 mol) of ethanol and 3.6 g (0.09 mol) of NaOH are put into a 4-neck reactor equipped with a thermometer, a condenser and a stirrer and the mixture is heated to 70 캜 while stirring. After 3 hours of reaction, the fatty acid ester (1) content was analyzed by GC analysis. The omega-7 fatty acid (palmitoleic acid) was 9 wt% and the conversion was 99.5%.
The preliminary distillation step (1) of the fatty acid ester (1)
The low boiling point components were condensed and recovered in a thin film distillation apparatus at a pressure of 0.001 mbar and a temperature of 130 ° C to 135 ° C. The recovered low boiling point component was analyzed by GC for fatty acid ester (2) content, and it was confirmed that omega-7 fatty acid (palmitoleic acid) was concentrated to 15% by weight.
The fractional distillation stage of the fatty acid ester (2)
1200 g of the fatty acid ester (2) was fed into a reactor equipped with a 40-stage distillation column, an upper condenser, a reflux device, a pressure reducing device and a pressure regulator, and the column was stabilized by refluxing at 10 torr (13.3 mbar) 3 to remove the low-boiling fraction, then convert to reflux ratio 10 and distill. The fatty acid ester (3) in which the upper temperature of the column is distilled at 184 ° C is obtained. When the temperature exceeds 185 ° C, the distillation is stopped and the high boiling fraction is recovered as the residue. From the GC analysis of the recovered fatty acid ester (3) component, it was confirmed that omega-7 fatty acid (palmitoleic acid) was concentrated to 39.6% by weight.
The first stage of separation and purification of the fatty acid ester (3)
120 g of the fatty acid ester (3), 240 g of urea and 770 g of methanol were charged into the reactor and the temperature was raised to 60 캜 to confirm that the urea was completely dissolved in methanol. Then, the reaction was slowly cooled to 15 캜 and stood for 30 minutes to precipitate urea crystals do. When the crystallization is completed, the reaction product is separated by filtration into urea crystals and a methanol solution, and then 500 g of a 10 wt% NaCl aqueous solution is added to the methanol solution to separate into a fatty acid ester (4) layer and a methanol / water / NaCl mixture layer. This is separated into layers. Purified water is added to the fatty acid ester (4) layer, which is then washed with water and deaerated to obtain a high purity fatty acid ester (4). From the GC analysis of the recovered fatty acid ester (4) component, it was confirmed that omega-7 fatty acid (palmitoleic acid) was concentrated to 63% by weight.
Secondary separation and purification step of fatty acid ester (4)
The fatty acid ester (4) was dissolved in methanol and separated and collected in an HPLC column according to the conditions shown in Table 2 below to remove methanol and recover the high purity omega-7 fatty acid (5).
The omega-7 fatty acid (palmitoleic acid) was concentrated to 93% by weight of the high purity omega-7 fatty acid component (5) through GC analysis, and the production yield was confirmed to be 63%.
[Table 2] HPLC operating conditions
[Example 2]
The procedure of Example 1 was repeated up to the ethanolysis step.
Preliminary distillation of fatty acid ester (1) Step-2
The fatty acid ester (1) was separated using a 20-stage continuous distillation apparatus. The operation pressure was 0.05 mbar, the reflux ratio was 1, the bottom boiler temperature was maintained at 163 ° C, and the temperature of the feed oil was maintained at 60 ° C To obtain a fatty acid ester (5).
The recovered fatty acid ester (5) component was confirmed by GC analysis to be concentrated to 20.0% by weight of omega-7 fatty acid (palmitoleic acid).
The first stage of separation and purification of the fatty acid ester (5)
120 g of the above fatty acid ester (5), 280 g of urea and 770 g of methanol were charged into the reactor, and the temperature was raised to 60 캜 to confirm that the urea was completely dissolved in methanol. Then, the reaction was gradually cooled to 15 캜 and stagnated for 30 minutes to precipitate urea crystals do. Upon completion of the crystallization, the reaction product is separated by filtration into urea crystals and a methanol solution, and 500 g of a 10 wt% NaCl aqueous solution is added to the methanol solution to separate into a fatty acid ester (6) layer and a methanol / water / NaCl mixture layer. Layer separation is carried out, and purified water is added to the fatty acid ester (6) layer, which is then washed with water and degassed to obtain a high purity fatty acid ester (6). From the GC analysis of the recovered fatty acid ester (6) component, it was confirmed that omega-7 fatty acid (palmitoleic acid) was concentrated to 48% by weight.
24 g of the recovered fatty acid ester (6) and 96 g of menhaden oil were mixed, and then the urea crystallization step was repeated to obtain a high purity fatty acid ester (7). GC analysis of the recovered fatty acid ester (7) component confirmed that the omega-7 fatty acid (palmitoleic acid) was concentrated to 58% by weight.
Secondary separation and purification step of fatty acid ester (7)
The fatty acid ester (7) was dissolved in methanol and then separated and collected in an HPLC column to remove methanol and recover high purity omega-7 fatty acid (8).
The high purity omega-7 fatty acid (8) component was concentrated to 91.8 wt% omega-7 fatty acid (palmitoleic acid) through GC analysis and the production yield was 39%.
[Comparative Example 1]
The omega-7 fatty acid (9) was obtained in the same manner as in Example 1 except that the first separation and purification (fatty acid crystallization) of the fatty acid ester was not carried out. The omega-7 fatty acid (9) component was concentrated to 90.6% by weight of omega-7 fatty acid (palmitoleic acid) through GC analysis, and the production yield was 27%.
As shown in Examples 1 and 2, it was found that omega-7 unsaturated fatty acids with high concentration and high purity can be selectively obtained by purification according to the manufacturing process of the present invention, and the production yield is also excellent.
While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.
Claims (10)
b) distilling the fatty acid ester to produce a concentrated fatty acid ester,
c) separating and concentrating the omega-7 fatty acid through a recrystallization process using the urea and the concentrated fatty acid esterified product;
and d) a step of subjecting the omega-7 fatty acid to secondary separation and purification through column chromatography to purify the omega-7 unsaturated fatty acid.
The purification process may further include a step of saponifying the natural fish oil before the step a) to pretreat the fatty acid to less than 1% by weight of the omega-7 unsaturated fatty acid.
The step a) is carried out at 60 to 80 ° C for 1 to 4 hours,
A process for purifying omega-7 unsaturated fatty acids in which ethanol is added in an amount of 50 to 300 equivalent% based on the natural fish oil equivalent.
The step b) is a purification process of the omega-7 unsaturated fatty acid which is carried out at 100-200 ° C and 0.001-20 mbar.
The step b)
b-1) preparing a first concentrated fatty acid ester product by preliminary distillation of the fatty acid ester prepared in the step a) with a short path distillation (SPD) device, and
b-2) Purifying the omega-7 unsaturated fatty acid comprising fractionally distilling the primary condensed fatty acid ester product to prepare a secondary enriched fatty acid esterified product.
The step b) may be performed using a thin-film molecular distillation or continuous distillation method,
Wherein the continuous distillation is a distillation at a reflux ratio of 1 to 10 using a 20 to 40-stage distillation column, and a purification process of the omega-7 unsaturated fatty acid.
In step c), 150 to 300 parts by weight of urea and 600 to 800 parts by weight of a solvent are mixed with 100 parts by weight of the omega-7 fatty acid at a temperature of 50 to 70 캜, and the solution is cooled to 10 to 20 캜 to precipitate urea crystals Purification process of omega-7 unsaturated fatty acids as a feature.
A process for purifying omega-7 unsaturated fatty acids by mixing the omega-7 fatty acid obtained in the step c) with menhaden oil and repeating the recrystallization step using the elements of step c).
The omega-7 unsaturated fatty acid which has undergone the purification process is palmitoleic acid and the concentration of the omega-7 unsaturated fatty acid is 90% by weight or more.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576064A (en) * | 2018-12-27 | 2019-04-05 | 国家海洋局第三海洋研究所 | The method for preparing trans- palmitoleic acid is separated from fish oil |
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| WO2020231075A1 (en) * | 2019-05-10 | 2020-11-19 | (주) 바이텍 | Omega-7-containing purified fish oil powder composition and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2273570A1 (en) | 1999-05-31 | 2000-11-30 | Jfs Envirohealth Ltd. | Concentration and purification of polyunsaturated fatty acid esters by distillation-enzymatic transesterification coupling |
| JP2010532418A (en) | 2007-06-29 | 2010-10-07 | マーテック バイオサイエンシーズ コーポレーション | Process for producing and purifying ester of polyunsaturated fatty acid |
| WO2015077499A1 (en) * | 2013-11-22 | 2015-05-28 | Heliae Development, Llc | Isolation of omega-7 fatty acid ethyl esters from natural oils |
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| KR20190064023A (en) * | 2017-11-30 | 2019-06-10 | (주)아모레퍼시픽 | Method for preparing fatty acid composition using natural wax and fatty acid composition prepared thereby |
| CN109576064A (en) * | 2018-12-27 | 2019-04-05 | 国家海洋局第三海洋研究所 | The method for preparing trans- palmitoleic acid is separated from fish oil |
| KR20200130148A (en) * | 2019-05-10 | 2020-11-18 | (주) 바이텍 | Purified Fish Oil Powder Compostion Containing Omega-7 Fatty Acid and Method for Preparing the Same |
| WO2020231075A1 (en) * | 2019-05-10 | 2020-11-19 | (주) 바이텍 | Omega-7-containing purified fish oil powder composition and preparation method therefor |
| KR20220067714A (en) * | 2020-11-18 | 2022-05-25 | 주식회사 엘에스엔지니어링 | High purity purification apparatus and purification method of docosahexaenoic acid or eicosapentaenoic acid |
| CN114133989A (en) * | 2021-11-30 | 2022-03-04 | 湖南成成油化科技股份有限公司 | Method for preparing and extracting palmitoleic acid and distillation device |
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| KR101815110B1 (en) | 2018-01-10 |
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