CN110857270A - High-content conjugated linoleic acid triglyceride and preparation method thereof - Google Patents
High-content conjugated linoleic acid triglyceride and preparation method thereof Download PDFInfo
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- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- 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
- C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
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Abstract
The invention relates to preparation of conjugated linoleic acid triglyceride, in particular to high-content conjugated linoleic acid triglyceride and a preparation method thereof. The invention increases the linoleic acid content to more than 95 percent by a crystallization purification method before the isomerization of the safflower oil methyl ester, and then obtains the conjugated linoleic acid triglyceride with high purity and high content by esterification reaction. The method has simple process, does not need the step of alkali-catalyzed transposition, and can greatly reduce the loss of the conjugated linoleic acid in the purification process and reduce the cost compared with the traditional process; in addition, the linoleic acid is purified and then conjugated, so that the proportion of two isomers (c9, t11-CLA) and (t10, c12-CLA) of the conjugated linoleic acid triglyceride can be kept at 1:1, and the purification method adopts a method of crystallization purification and high vacuum rectification, so that the linoleic acid is purified to more than 95 percent, has good application prospect and is suitable for large-scale application.
Description
Technical Field
The invention relates to preparation of conjugated linoleic acid triglyceride, in particular to a preparation method of high-quality and high-purity conjugated linoleic acid triglyceride.
Background
In the prior art, natural vegetable oil rich in linoleic acid is mainly adopted to prepare the conjugated linoleic acid, for example, the safflower oil is prepared into the conjugated linoleic acid by an alkali catalytic isomerization method, or the safflower oil is isomerized after alcoholysis and hydrolyzed to obtain the conjugated linoleic acid, the conjugated linoleic acid is lost in the purification process by the two methods, and the purity of the conjugated linoleic acid is reduced.
Chinese patent application CN107216249A discloses a method for preparing high-quality conjugated linoleic acid, which uses fatty acid short-chain alcohol ester as raw material to prepare conjugated linoleic acid through base-catalyzed isomerization reaction and saponification reaction. Although this solution solves the problem of the strong dependence of the conjugated linoleic acid content on the raw material, it must involve a base-catalyzed translocation step followed by purification, a process which entails loss of conjugated linoleic acid. Therefore, there is a need in the art for a method for preparing high-quality and high-purity conjugated linoleic acid.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides a high-content conjugated linoleic acid triglyceride and a preparation method thereof. The method has simple process and low cost, and can purify the conjugated linoleic acid triglyceride to more than 95%.
The invention adopts the following technical scheme that a preparation method of high-content conjugated linoleic acid triglyceride specifically comprises the following steps:
s1, crystallization and purification
Placing safflower oil methyl ester at-16-4 deg.C, maintaining for more than 10 hr, and filtering at low temperature to separate crystal and filtrate. Preferably, the safflower oil methyl ester is purified by subjecting to a low temperature of 2 ℃.
S2, rectification and purification
The bottom of the rectifying tower is connected with a thin film evaporator, the height of the tower is more than 1m, and the number of theoretical plates is not less than 30. Controlling the temperature of the thin film evaporator to be more than 200 ℃, keeping vacuum stability for 30min after reflux appears at the tower top, starting a condenser at the tower top, setting the reflux ratio to be at least 3:1, and collecting fractions to obtain purified safflower oil methyl ester.
S3. conjugation reaction
Under the vacuum condition, adding a potassium methoxide methanol solution with the mass of 10 percent of that of the safflower oil methyl ester dropwise into the purified safflower oil methyl ester, heating to 105-110 ℃ for conjugation reaction to obtain conjugated linoleic acid methyl ester;
more specifically, the conjugation reaction step is: under vacuum, a 10% methanol solution of potassium methoxide based on the weight of safflower oil methyl ester was added dropwise to the purified safflower oil methyl ester. The temperature is raised to 105-110 ℃. And after the reaction is qualified, cooling to 80 ℃, adding methanol, cooling to 45 ℃, adjusting the pH to 7-8 by using a methanol sulfate solution, adding sodium bisulfate accounting for 2% of the weight of the safflower oil methyl ester, starting steam, heating and refluxing, controlling the steam pressure to be less than 2.0MPa and the reflux temperature to be 65-75 ℃, continuously reacting for 1h, and removing the catalyst sodium bisulfate to obtain the conjugated methyl linoleate. The judgment standard of qualified reaction is as follows: and when the residual amount of the linoleic acid is less than or equal to 1.5 percent, judging that the reaction is qualified.
S4, esterification reaction
Adding glycerol triacetate with the mass of 0.18-0.25 times (preferably 0.22 times) of safflower oil methyl ester into conjugated linoleic acid methyl ester, mixing, vacuumizing, controlling nitrogen flow, and stabilizing at 15-20m3H, heating to 90 ℃. Dropwise adding sodium methoxide methanol solution with the mass of 2.5-4.0% (preferably 3.0%) of safflower oil methyl ester at a small flow rate, controlling the adding time to be finished for 30min, heating to 130-135 ℃, and carrying out heat preservation reaction for 7-10 h. After the reaction is finished, the nitrogen is broken. Cooling to 45 ℃, adding water in an amount which is 1 time of the weight of the safflower oil methyl ester into the kettle for washing until the Ph of a water layer is 6-7, heating to 80 ℃, and removing water.
S5, collecting
Starting a heat transfer oil system, controlling the temperature of the reaction kettle at 175-.
In the step S3, the method for removing the catalyst sodium bisulfate specifically comprises: and (3) evaporating methanol at normal pressure, simultaneously replenishing methanol into the kettle, heating until reflux appears in the kettle, and continuing to react for 1 hour. Adding water 0.3 times the weight of safflower oil methyl ester into the kettle, stirring for 20 minutes, and standing to remove acid water layer. Adding water 0.2 times the weight of safflower oil methyl ester into the kettle, and stirring for 20 minutes until the Ph of the water layer is 6-7. Stirring, heating to 100 deg.C, and removing water under reduced pressure.
Another object of the present invention is to claim the conjugated linoleic acid triglyceride obtained by the above process, wherein the ratio of the two isomers (c9, t11-CLA) to (t10, c12-CLA) is maintained at 1: 1.
The content of linoleic acid in safflower oil methyl ester is about 80%, but the safflower oil methyl ester contains fatty acids such as palmitic acid, stearic acid, oleic acid and the like in addition to linoleic acid, therefore, the direct preparation of linoleic acid with a certain purity by taking safflower oil methyl ester as a raw material increases the consumption of the raw material and improves the production cost, in addition, in the traditional process, the proportion of the safflower oil methyl ester isomer meeting the production requirements is difficult to maintain, the invention skillfully adjusts the process sequence, the linoleic acid content is increased to more than 95 percent by a crystallization purification method before the isomerization of the safflower oil methyl ester, then high-purity and high-content conjugated linoleic acid triglyceride is obtained by esterification reaction, the method can obviously improve the loss of the conjugated linoleic acid caused by purification after isomerization in the traditional process, not only saves the isomerization cost, but also more importantly improves the quality of the conjugated linoleic acid triglyceride.
Has the advantages that: the method has simple process, does not need the step of alkali-catalyzed transposition, and can greatly reduce the loss of the conjugated linoleic acid in the purification process and reduce the cost compared with the traditional process; in addition, the linoleic acid is purified and then conjugated, so that the proportion of two isomers (c9, t11-CLA) and (t10, c12-CLA) of the conjugated linoleic acid triglyceride can be kept at 1:1, and the purification method adopts a method of crystallization purification and high vacuum rectification, so that the linoleic acid is purified to more than 95 percent, has good application prospect and is suitable for large-scale application.
Drawings
FIG. 1 is a liquid phase spectrum of the product of example 1.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
S1, putting 1450L of methyl safflower oil into a kettle, placing the kettle in a refrigerator, setting the temperature of the refrigerator to be 2 ℃, placing the kettle for 24 hours, keeping the low temperature condition unchanged, and extracting liquid from the upper layer.
S2, putting the extracted liquid into a kettle, heating to 220 ℃, pumping into a film evaporator, controlling the temperature of the film evaporator to be more than 200 ℃, setting a gear pump to be 20HZ, setting feeding frequency according to the discharging condition, stabilizing for 30min after reflux appears at the top of the tower, opening a valve of a receiving tank, controlling the reflux ratio to be 10:1, and collecting fractions. The height of the tower is 9m, the number of theoretical plates is 30-50, a condenser at the top of the tower is started, the reflux ratio is set to be at least 3:1, fractions are collected, and purified safflower oil methyl ester is obtained.
S3, putting 1200kg of purified safflower oil methyl ester into a kettle, and dripping 125kg of potassium methoxide methanol solution while vacuumizing. After the dropping is finished, the temperature is raised to 105-110 ℃, and the stirring is continued for 1 h. And after the reaction is qualified, cooling to 80 ℃, adding 200ml of methanol, continuously cooling to 45 ℃, adding 28kg of sulfuric acid and 400ml of methanol, adjusting the Ph to be 7-8, adding 25kg of sodium bisulfate into the kettle, starting steam to heat and reflux, controlling the steam pressure to be less than 2.0MPa, controlling the reflux temperature to be 65-75 ℃, continuously reacting for 1h, evaporating the methanol at normal pressure, simultaneously supplementing 300L of methanol into the kettle, heating until reflux appears in the kettle, controlling the reflux temperature to be 65-75 ℃, and continuously reacting for 1 h. 300L of water was added to the kettle, stirred for 20 minutes, and allowed to stand to separate the acid water layer. 200L of water is added into the kettle each time, and the mixture is stirred for 20 minutes until the pH value of the water layer is 7-8. Stirring, heating to 100 deg.C, and removing water under reduced pressure.
S4, mixing 1250kg of qualified reacted conjugated methyl linoleate with 276kg of glycerol triacetate, vacuumizing, controlling the nitrogen flow to be stable at 15-20m3H, heating to 90 ℃. Dropwise adding 33kg of sodium methoxide methanol solution at a small flow rate, controlling the adding time to be finished for 30min, starting steam, slowly heating to 130-The reaction is carried out for 8 h. After the reaction is finished, the nitrogen is broken. Cooling to 45 ℃, adding 750L of water and 500L of methanol into the kettle, stirring for 20 minutes, standing to separate a water layer, adding 750L of water and 500L of methanol again, stirring for 20 minutes, standing to separate a water layer until the pH value of the water layer is 6-7, heating to 80 ℃, and removing water.
S5, starting the heat-conducting oil system, controlling the temperature at 175-190 ℃, opening the cold well, and opening the vacuum unit, wherein the system pressure is less than 20 Pa. Starting short-distance stirring, starting feeding, stabilizing the feeding temperature at 100-120 ℃, controlling the feeding amount at 60-140L/h, and collecting heavy components. As can be seen from FIG. 1, the total conjugated linoleic acid triglyceride content is 95% to 97%.
Comparative example 1
Using fatty acid with conjugated linoleic acid content of at least 55% as raw material, preferably the raw material with palmitic acid content of less than 5%, cooling the fatty acid to-5-10 deg.C, and keeping for 20-500 hr. The precipitate is then separated by filtration, centrifugation, decantation or a combination thereof, after which the solid is pressed one or more times by means of a filter press. The yield thereof was found to be 85%.
Comparative example 2
In contrast to the method disclosed in chinese patent application CN102559389A, a CLA composition was prepared according to the method of this application example 1, 900 kg of the composition was cooled to-3 to 3 ℃ in a container for 72 hours. White crystals appeared and settled at the bottom of the vessel and the upper layer was decanted. The lower layer was transferred to a filter press pack and separated using a hydraulic vertical press. The pressing was repeated twice. The olein (liquid) fraction from the press and the upper layer are combined and pumped to a bleaching vessel to bleach the oil. The product thus obtained contained 79.1% by weight of CLA and 6.4% by weight of SAFA and was obtained in an overall yield of 90% by weight.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (8)
1. A preparation method of high-content conjugated linoleic acid triglyceride is characterized by comprising the following steps:
s1, crystallization and purification
Placing safflower oil methyl ester at-16-4 deg.C, maintaining for more than 10 hr, filtering at low temperature to separate crystal and filtrate;
s2, rectification and purification
Connecting a thin film evaporator at the bottom of the rectifying tower, wherein the height of the tower is more than 1m, the number of theoretical plates is not less than 30, controlling the temperature of the thin film evaporator to be more than 200 ℃, keeping vacuum stability for 30min after reflux appears at the top of the tower, starting a condenser at the top of the tower, setting the reflux ratio to be at least 3:1, and collecting fractions to obtain purified safflower oil methyl ester;
s3. conjugation reaction
Under the vacuum condition, adding a potassium methoxide methanol solution with the mass of 10 percent of that of the safflower oil methyl ester dropwise into the purified safflower oil methyl ester, heating to 105-110 ℃ for conjugation reaction to obtain conjugated linoleic acid methyl ester;
s4, esterification reaction
Adding glycerol triacetate with the mass 0.22 time that of safflower oil methyl ester into conjugated methyl linoleate to mix, heating to 90 ℃ under the protection of nitrogen to react, then dropwise adding sodium methoxide methanol solution with the mass 3.0% of safflower oil methyl ester, heating to 130-135 ℃, keeping the temperature to react for 7-10h, washing after the reaction is finished until the pH value of a water layer is 6-7, heating to 80 ℃, and removing water;
s5, collecting
Starting a heat transfer oil system, controlling the temperature of the reaction kettle at 175-190 ℃, the system pressure at less than 20Pa, the feeding temperature at 100-120 ℃, and the feeding amount at 60-140L/h, and collecting the heavy components to obtain the conjugated linoleic acid triglyceride.
2. The method according to claim 1, wherein said step S1 of purifying safflower oil methyl ester is carried out at a low temperature of 2 ℃.
3. The method according to claim 1, wherein the conjugation reaction of step S3 is specifically: under the vacuum condition, adding a potassium methylate methanol solution which is 10 percent of the mass of the safflower oil methyl ester into the purified safflower oil methyl ester dropwise, heating to 105-110 ℃, cooling to 80 ℃ after the reaction is qualified, adding methanol, cooling to 45 ℃, adjusting the pH to 7-8, adding sodium bisulfate which is 2 percent of the mass of the safflower oil methyl ester, starting steam, heating and refluxing, and removing the catalyst sodium bisulfate to obtain the conjugated linoleic acid methyl ester.
4. The method of claim 1, wherein in the step S3, during steam heating reflux, the steam pressure is controlled to be less than 2.0MPa, the reflux temperature is controlled to be 65-75 ℃, and after the reaction is continued for 1h, the catalyst sodium bisulfate is removed.
5. The method according to claim 1, wherein the esterification reaction of step S4 is specifically: adding glycerol triacetate 0.18-0.25 times of safflower oil methyl ester into conjugated linoleic acid methyl ester, mixing, vacuumizing, and controlling nitrogen flow to be 15-20m3Heating to 90 ℃, dropwise adding a sodium methoxide methanol solution with the mass of 2.5-4.0% of safflower oil methyl ester, heating to 130-.
6. The method according to claim 1, wherein in step S3, the method for removing the catalyst sodium bisulfate is specifically as follows: distilling out methanol at normal pressure, simultaneously replenishing methanol into the kettle, heating until reflux appears in the kettle, continuing to react for 1h, adding water which is 0.3 times of the weight of the safflower oil methyl ester into the kettle, stirring for 20 min, standing to separate an acid water layer, adding water which is 0.2 times of the weight of the safflower oil methyl ester into the kettle each time, and stirring for 20 min until the Ph of the water layer is 6-7. Stirring, heating to 100 deg.C, and removing water under reduced pressure.
7. A conjugated linoleic acid triglyceride produced according to the method of claim 1.
8. The conjugated linoleic acid triglyceride according to claim 7, wherein the ratio of the two isomers (c9, t11-CLA) and (t10, c12-CLA) of the conjugated linoleic acid triglyceride is 1: 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580030A (en) * | 2003-08-04 | 2005-02-16 | 刘朝燊 | Method for synthesizing conjugated linoleic acid |
| CN102584586A (en) * | 2012-02-07 | 2012-07-18 | 大连医诺生物有限公司 | Preparation method of conjugated linoleic acid glycerides |
| CN104673499A (en) * | 2013-11-28 | 2015-06-03 | 丰益(上海)生物技术研发中心有限公司 | Method for preparing conjugated linoleic acid |
| CN106350233A (en) * | 2016-08-24 | 2017-01-25 | 哈尔滨普润油脂有限公司 | Preparation method of high-quality ethyl linolenate |
| CN107118099A (en) * | 2017-06-09 | 2017-09-01 | 安徽农业大学 | A kind of method for preparing CLA short-chain alcohol ester |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580030A (en) * | 2003-08-04 | 2005-02-16 | 刘朝燊 | Method for synthesizing conjugated linoleic acid |
| CN102584586A (en) * | 2012-02-07 | 2012-07-18 | 大连医诺生物有限公司 | Preparation method of conjugated linoleic acid glycerides |
| CN104673499A (en) * | 2013-11-28 | 2015-06-03 | 丰益(上海)生物技术研发中心有限公司 | Method for preparing conjugated linoleic acid |
| CN106350233A (en) * | 2016-08-24 | 2017-01-25 | 哈尔滨普润油脂有限公司 | Preparation method of high-quality ethyl linolenate |
| CN107118099A (en) * | 2017-06-09 | 2017-09-01 | 安徽农业大学 | A kind of method for preparing CLA short-chain alcohol ester |
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