CN110305015B - Separation method of natural partial glyceride - Google Patents
Separation method of natural partial glyceride Download PDFInfo
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- CN110305015B CN110305015B CN201910694135.5A CN201910694135A CN110305015B CN 110305015 B CN110305015 B CN 110305015B CN 201910694135 A CN201910694135 A CN 201910694135A CN 110305015 B CN110305015 B CN 110305015B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses a method for separating natural partial glyceride, which is to carry out twice elution treatment by taking vegetable oil as a raw material and taking a mixed solvent as an eluent through silica gel-alumina mixed filler column chromatography to remove the solvent, thereby obtaining a natural partial glyceride product with high purity (98-99.9%), few impurities (triglyceride content < 0.1%, free fatty acid content < 0.05%), light color and low oxidation index (acid value <0.1, peroxide value < 1.0). The method has the advantages of simple process, less filler and eluent, high product purity, and suitability for industrial production.
Description
Technical Field
The invention relates to a separation method of natural partial glyceride, belonging to the technical field of food and pharmaceutical engineering.
Background
The partial glyceride in natural vegetable oil comprises diglyceride and monoglyceride, and the monoglyceride content is very small, and the diglyceride is mainly present. Diacylglycerol (DAG) is a structural lipid formed by replacing one fatty acid of triglyceride by hydroxyl, and two isomers of 1, 3-diglyceride and 1, 3-diglyceride mainly exist, and are natural ingredients existing in grease. Diglyceride is a Generally Recognized As Safe (GRAS) food component, has no difference in taste and flavor from common triglyceride, can be used for producing food or health food instead of common oil, and has the effects of inhibiting weight gain and reducing blood fat.
At present, diglyceride is mainly prepared by methods such as a chemical synthesis method, an enzyme catalysis method, a glyceride hydrolysis method and the like, the content of the diglyceride obtained by the methods is 10-80%, but fatty acid, glycerol and other raw materials and lipase and other substances are required to be added in the preparation process of the diglyceride, so that the generation of byproducts is increased, new impurities are introduced, the quality risk is increased, and the separation difficulty is improved. For further purification, molecular distillation, solvent crystallization, fractionation, chromatography, etc. are usually employed. The molecular distillation method has high requirements on equipment, generally needs high-temperature conditions, and is difficult to control acid value and peroxide value; the solvent crystallization and extraction method needs to control low temperature to separate out diglyceride, and has the same requirements on equipment, large energy consumption and long time; the common chromatography usually uses silica gel as an adsorbent, and although the operation is simple, the filler amount is large, the separation effect is poor, a large amount of solvent is required for elution, and the large-scale application is difficult.
A method for preparing high-purity 1, 3-dioleic acid diglyceride by silica gel column chromatography is reported in the literature (research on high-purity 1, 3-dioleic acid diglyceride by Songzhilia, Shangshan, Huangjianhua, and the like [ J ] Chinese oil, 2015,40(12):70-73.) and although the purity of the prepared diglyceride reaches 98.03%, a large amount of silica gel is needed, the amount of the silica gel is 40 times of the previous amount, and the recovery rate is low (69.9%).
The vegetable oil contains a certain amount of natural partial glyceride, and the existing technology has great separation difficulty and high cost for partial glyceride in small amount in the vegetable oil, so the preparation method of directly separating partial glyceride by using the vegetable oil as a raw material is rare.
Disclosure of Invention
The invention aims to provide a method for separating natural partial glyceride, which is used for obtaining a natural partial glyceride product by carrying out elution treatment twice on vegetable oil serving as a raw material through mixed filler column chromatography and using a binary mixed solvent as an eluant, and removing the solvent, and solves the problems of high separation difficulty, high cost, low purity and the like of the conventional natural partial glyceride.
Another objective of the present invention is to provide a natural partial glyceride product obtained by the separation method of natural partial glyceride, which has high purity (98% -99.9%), few impurities (triglyceride content < 0.1%, free fatty acid content < 0.05%), light color, low oxidation index (acid value <0.1, peroxide value <1.0), and is used for food or health food production, and can improve the framework composition of edible oil for people.
In order to solve the technical problems, the invention adopts the following technical scheme:
a separation method of natural partial glyceride comprises performing secondary elution treatment on vegetable oil as raw material by mixed packed column chromatography with mixed solvent as eluent, and removing solvent to obtain natural partial glyceride product; the filler of the mixed filler column comprises silica gel and alumina.
The invention discloses a method for separating partial glyceride by taking vegetable oil as a raw material and carrying out column chromatography on the vegetable oil by using a silica gel and alumina mixed filler. The aluminum oxide is an amphoteric metal oxide, has a unique electronic space structure, forms a Lewis acid-base center on the surface of the aluminum oxide, and has the characteristics of physical adsorption and chemical adsorption on an acidic compound. On the other hand, the aluminum oxide and the silica gel are used as the mixed adsorption filler, so that the adsorption-desorption process of the polar compound is optimized. Therefore, the mixed filler not only makes up the defects of single silica gel, Florisil or other adsorbents, enhances the separation effect of partial glyceride, reduces the using amount of the adsorbent filler and the using amount of the eluent, and simultaneously achieves the beneficial effects of reducing impurities and pigments, reducing acid value and peroxide value and the like.
Further, the weight ratio of the silica gel to the alumina is 0.5: 1-16: 1.
Further, the weight ratio of the filler to the raw materials is 0.25: 1-10: 1.
Further, the mixed solvent comprises a solvent A and a solvent B; the solvent A is one of n-hexane, n-heptane and petroleum ether; the solvent B is one of ethyl acetate and diethyl ether.
Further, when the first elution in the second elution is performed, the solvent B accounts for 0-10% of the mixed solvent.
Further, when the second elution in the second elution treatment is performed, the solvent B accounts for 5-50% of the mixed solvent.
Further, when the first elution in the second elution is performed, the volume-to-weight ratio of the eluent to the raw material is 3:1 to 25:1 (L/kg).
Further, when the second elution in the second elution treatment is performed, the volume-to-weight ratio of the eluent to the raw material is 2:1 to 20:1 (L/kg).
Further, the raw material comprises one or more of olive oil, soybean oil, rapeseed oil, tea seed oil, palm oil and peanut oil.
A natural partial glyceride product obtained by the separation method of the natural partial glyceride.
The implementation of the invention has the following beneficial effects:
(1) the natural partial glyceride separated by the method has high purity, has the characteristics of low impurity content, light color and even colorless, and low acid value and peroxide value, and is convenient to apply to the aspects of food, medicine and the like.
(2) Compared with the prior art, the method directly separates and prepares the natural partial glyceride from the vegetable oil for the first time, and avoids the problem of introducing new impurities due to the chemical or enzymatic synthesis of diglyceride.
(3) Compared with the prior art, the mixed adsorbent filler is adopted, so that the separation effect of partial glyceride is improved, the using amount of the adsorbent is reduced, the defects of poor separation and large using amount of a single filler are overcome, and the effects of effectively controlling impurities and reducing the acid value and the peroxide value are achieved.
(4) The invention reasonably adjusts the polarity of the eluent by eluting twice with the mixed solvent, greatly reduces the dosage of the eluent, can be recycled for multiple times, is environment-friendly and saves the cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to specific embodiments.
Example 1
Taking 1kg of soybean oil, filling 0.5kg of mixed adsorbent (silica gel/alumina mass ratio is 2:1) for column chromatography, after the oil naturally flows out (or properly pressurizing (0.01-0.1 MPa)), eluting 20L with an eluent (99% ethyl acetate of n-hexane and 1%) for the first time, eluting 16L with an eluent (95% ethyl acetate of n-hexane and 5%) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural soybean partial glyceride product which is light yellow, has the purity of 99.3%, the content of triglyceride of less than 0.1%, the content of free fatty acid of less than 0.05%, the acid value of 0.08 and the peroxide value of 0.76.
Example 2
Taking 1kg of soybean oil, filling 1.0kg of mixed adsorbent (silica gel/alumina mass ratio is 3:1) for column chromatography, after the oil naturally flows out (or properly pressurizing (0.01-0.1 MPa)), eluting 23L with eluent (98% ethyl acetate in n-hexane and 2%) for the first time, eluting 18L with eluent (95% ethyl acetate in n-hexane and 5%) for the second time, collecting the eluent for the second time, and carrying out vacuum concentration and drying to obtain a natural soybean partial glyceride product which is colorless, has the purity of 99.8%, the content of triglyceride of less than 0.1%, the content of free fatty acid of less than 0.05%, the acid value of 0.05 and the peroxide value of 0.63.
Example 3
Taking 1kg of olive oil, filling 0.5kg of mixed adsorbent (silica gel/alumina mass ratio is 4:1), performing column chromatography, after the oil naturally flows out (properly pressurizing (0.01-0.1 MPa)), eluting 20L with eluent (97% ethyl acetate of normal hexane and 3%) for the first time, eluting 16L with eluent (90% ethyl acetate of normal hexane and 10%) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural olive oil partial glyceride product which is colorless, has the purity of 99.2%, the triglyceride content of less than 0.1%, the free fatty acid content of less than 0.05%, the acid value of 0.06 and the peroxide value of 0.58.
Example 4
Taking 1kg of olive oil, filling 0.5kg of mixed adsorbent (silica gel/alumina mass ratio is 4:1), performing column chromatography, after the oil naturally flows out (properly pressurizing (0.01-0.1 MPa)), eluting 18L with eluent (99% of diethyl ether 1%) for the first time, eluting 16L with eluent (95% of diethyl ether 5%) for the second time, collecting eluent for the second time, and performing vacuum concentration and drying to obtain a natural olive oil partial glyceride product which is colorless, has the purity of 99.7%, the content of triglyceride of less than 0.1%, the content of free fatty acid of less than 0.05%, the acid value of 0.03 and the peroxide value of 0.58.
Example 5
Taking 1kg of rapeseed oil, filling 2.0kg of mixed adsorbent (silica gel/alumina mass ratio is 5:1), carrying out column chromatography, after oil naturally flows out (under proper pressure (0.01-0.1 MPa)), eluting 25L with eluent (97% of diethyl ether in n-hexane) for the first time, eluting 20L with eluent (93% of diethyl ether in n-hexane) for the second time, collecting eluent for the second time, carrying out vacuum concentration and drying to obtain a partial glyceride product of the natural rapeseed oil, wherein the partial glyceride product is colorless, the purity is 99.3%, the triglyceride content is less than 0.1%, the free fatty acid content is less than 0.05%, the acid value is 0.06, and the peroxide value is 0.62.
Example 6
Dissolving 1kg of rapeseed oil with a proper amount of n-heptane, filling 2.5kg of mixed adsorbent (silica gel/alumina mass ratio is 4:1) for column chromatography, after the oil naturally flows out (under proper pressure (0.01-0.1 MPa)), eluting 12L with an eluent (n-heptane 92% ethyl acetate 8%) for the first time, eluting 15L with an eluent (n-heptane 85% ethyl acetate 15%) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a partial glyceride product of the natural rapeseed oil, wherein the partial glyceride product is colorless, has the purity of 99.1%, the triglyceride content of less than 0.1%, the free fatty acid content of less than 0.05%, the acid value of 0.08 and the peroxide value of 0.88.
Example 7
Dissolving 1kg of tea seed oil with a proper amount of n-heptane, filling 2.0kg of mixed adsorbent (silica gel/alumina mass ratio is 5:1) for column chromatography, eluting 18L with an eluent (n-heptane 95% ethyl acetate 5%) for the first time and 16L with an eluent (n-heptane 85% ethyl acetate 15%) for the second time after the oil naturally flows out (under proper pressure (0.01-0.1 MPa)), collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural tea seed oil partial glyceride product with colorless purity of 98.9%, triglyceride content of less than 0.1%, free fatty acid content of less than 0.05%, acid value of 0.08 and peroxide value of 0.45.
Example 8
Taking 1kg of tea seed oil, filling 4.0kg of mixed adsorbent (silica gel/alumina mass ratio is 3:1), performing column chromatography, after oil naturally flows out (properly pressurizing (0.01-0.1 MPa)), eluting 23L with eluent (petroleum ether 95% diethyl ether 5%) for the first time, eluting 20L with eluent (petroleum ether 85% diethyl ether 15%) for the second time, collecting eluent for the second time, and performing vacuum concentration and drying to obtain a natural tea seed oil partial glyceride product which is colorless, has the purity of 98.7%, the content of triglyceride of less than 0.1%, the content of free fatty acid of less than 0.05%, the acid value of 0.06 and the peroxide value of 0.53.
Example 9
Taking 1kg of olive oil, filling 2.5kg of mixed adsorbent (silica gel/alumina mass ratio is 0.5:1), performing column chromatography, after the oil naturally flows out (properly pressurized (0.01-0.1 MPa)), eluting for the first time by using an eluent (n-hexane 95% ethyl acetate 5%) for 23L, eluting for the second time by using an eluent (n-hexane 85% ethyl acetate 15%) for 20L, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural olive oil partial glyceride product which is colorless, has the purity of 98.6%, the triglyceride content of less than 0.5%, the free fatty acid content of less than 0.05%, the acid value of 0.03 and the peroxide value of 0.98.
Example 10
Taking 1kg of olive oil, filling 2.5kg of mixed adsorbent (silica gel/alumina mass ratio is 16:1), performing column chromatography, after the oil naturally flows out (properly pressurizing (0.01-0.1 MPa)), eluting 23L with eluent (n-hexane 95% ethyl acetate 5%) for the first time, eluting 20L with eluent (n-hexane 85% ethyl acetate 15%) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural olive oil partial glyceride product which is light yellow, has the purity of 98.8%, the triglyceride content of 0.51%, the free fatty acid content of less than 0.05%, the acid value of 0.13 and the peroxide value of 0.45.
Comparative example 1
Taking 1kg of soybean oil, filling 4.0kg of silica gel for column chromatography, after the oil naturally flows out (under proper pressure (0.01-0.1 MPa)), eluting 40L with an eluent (95% ethyl acetate 5% n-hexane) for the first time, eluting 42L with an eluent (85% ethyl acetate 15% n-hexane) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural soybean oil partial glyceride product with faint yellow color, the purity of 96.6%, the triglyceride content of 3.58%, the free fatty acid content of 0.62%, the acid value of 1.23 and the peroxide value of 0.83.
Comparative example 2
Taking 1kg of soybean oil, filling 4.0kg of alumina for column chromatography, after the oil naturally flows out (under proper pressurization (0.01-0.1 MPa)), eluting 45L with an eluent (n-hexane 95% ethyl acetate 5%) for the first time, eluting 45L with an eluent (n-hexane 85% ethyl acetate 15%) for the second time, collecting the eluent for the second time, and performing vacuum concentration and drying to obtain a natural soybean oil partial glyceride product with faint yellow color, purity of 95.7%, triglyceride content of 4.17%, free fatty acid content of less than 0.05%, acid value of 0.03 and peroxide value of 1.67.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (7)
1. A separation method of natural partial glyceride is characterized in that vegetable oil is used as a raw material, secondary elution treatment is carried out by mixed packed column chromatography and mixed solvent is used as an eluant, and the solvent is removed to obtain a natural partial glyceride product; the filler of the mixed filler column comprises silica gel and alumina; the mixed solvent comprises a solvent A and a solvent B; the solvent A is one of n-hexane, n-heptane and petroleum ether; the solvent B is one of ethyl acetate and diethyl ether; when the first elution in the secondary elution treatment is carried out, the solvent B accounts for 0-10% of the mixed solvent; and when the second elution in the secondary elution treatment is carried out, the solvent B accounts for 5-50% of the mixed solvent.
2. The method for separating natural partial glyceride according to claim 1, wherein the weight ratio of the silica gel to the alumina is 0.5:1 to 16: 1.
3. The method for separating natural partial glyceride according to claim 1, wherein the weight ratio of the filler to the raw material is 0.25:1 to 10: 1.
4. The method for separating natural partial glyceride according to claim 1, wherein the volume weight ratio of the eluent to the raw material is 3:1 to 25:1L/kg when the first elution in the second elution is performed.
5. The method for separating natural partial glyceride according to claim 1, wherein the volume weight ratio of the eluent to the raw material is 2:1 to 20:1L/kg when the second elution is performed in the second elution treatment.
6. The method of claim 1, wherein the raw material comprises one or more of olive oil, soybean oil, rapeseed oil, tea seed oil, palm oil, peanut oil, and sunflower seed oil.
7. A natural partial glyceride product obtained by the method for separating a natural partial glyceride according to any one of claims 1 to 6.
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