CN112430500A - Method for reducing anisidine value in polyunsaturated fatty acid oil - Google Patents
Method for reducing anisidine value in polyunsaturated fatty acid oil Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/006—Refining fats or fatty oils by extraction
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
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Abstract
The invention provides a method for reducing anisidine value in polyunsaturated fatty acid oil, which comprises the steps of dissolving a polyunsaturated fatty acid raw material in an organic solvent, adding an adsorbent, stirring and adsorbing at a lower temperature, filtering to remove the adsorbent, drying liquid components in the adsorbent by using inert gas, recovering the organic solvent in filtrate to obtain a crude product, and obtaining the polyunsaturated fatty acid oil with the low anisidine value after molecular distillation or rectification of the crude product. The method has the advantages that the consumption of the adsorbent is low in the process, the effect of reducing the anisidine value is obvious, the loss of the polyunsaturated fatty acid is low, the polyunsaturated fatty acid oil obtained as the final product has no peculiar smell, the consumer demand can be well met, the peroxide value and the anisidine value of the final product can be effectively reduced by the adsorbent applied or added in the production process, and a certain removing effect is realized on other trace substances in the product, such as color, heavy metal, dioxin, benzopyrene and the like.
Description
Technical Field
The invention mainly describes a method for efficiently reducing the anisidine value of polyunsaturated fatty acid oil by an adsorption method. Belongs to the field of biochemical engineering.
Background
As people pay more attention to their health, the public starts to ingest more nutritional and healthy dietary supplements, and polyunsaturated fatty acid (PUFA) products play an important role.
Polyunsaturated fatty acid (PUFA) is an important material basis in body metabolism, particularly in activities such as infant brain development and the like, is a constituent component of cell membranes, mainly plays a role in keeping cell membrane fluidity, promoting cholesterol esterification, reducing cholesterol and triglyceride, reducing blood viscosity, improving physiological functions such as blood circulation and the like, and also has the functions of improving human thinking, enhancing memory and the like. On the other hand, polyunsaturated fatty acid (PUFA) substances cannot be synthesized by the human body itself and must be obtained by ingestion of a meal or the like.
Polyunsaturated fatty acids (PUFA) are in various types, mainly including omega-3 polyunsaturated fatty acids (PUFA) (omega-3 PUFA), omega-6 polyunsaturated fatty acids (PUFA) (omega-6 PUFA), omega-9 polyunsaturated fatty acids (PUFA) (omega-9 PUFA) and the like, such as alpha-linolenic acid (ALA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), docosapentaenoic acid (DPA), Linoleic Acid (LA), Conjugated Linoleic Acid (CLA), gamma-linolenic acid (GLA), Arachidonic Acid (AA) and the like, wherein especially the omega-3 polyunsaturated fatty acids (omega-3 PUFA) mainly represented by eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are most widely known and accepted, and have the most obvious effects of improving and promoting the health of human bodies and animals, the molecular structural formula of the partially polyunsaturated fatty acid material is as follows:
due to the structural characteristics of more unsaturated bonds of PUFA, the PUFA is very easy to generate oxidation reaction in the processing and storage processes to form hydroperoxide (primary oxidation product, peroxide value is taken as evaluation index), the hydroperoxide is very unstable and can be further decomposed to form compounds such as aldehyde and ketone (secondary oxidation product, anisidine value is taken as evaluation index), the aldehyde and ketone compounds are not only key substances forming polyunsaturated fatty acid rancid and fishy smell (micromolecule aldehyde volatilizes to generate fishy smell, peroxide generates rancid smell), the adverse stomach and nausea and vomiting of consumers are often caused, but also lipid peroxide and free radicals are generated by promoting the oxidation of fat in vivo after entering human bodies to cause the tissue lesion of cardiovascular and cerebrovascular vessels and the aging of human bodies, and toxic and side effects of carcinogenesis, promoting the rise of blood pressure, destroying the absorption of human bodies to fat-soluble vitamins and the like are also generated, is very harmful to human health, which limits the application of polyunsaturated fatty acids such as fish oil, conjugated linoleic acid and the like in medicines and health-care foods.
The content of aldehyde compounds in the polyunsaturated fatty acid oil is generally expressed by an Anisidine Value (AV), and the larger the value is, the more the degree of deterioration of the polyunsaturated fatty acid oil becomes, and the more the fishy smell or the unpleasant taste becomes noticeable. The standard limit for anisidine values of fish oil polyunsaturated fatty acids in the united states pharmacopeia and european pharmacopeia is below 20. However, in order to ensure the oxidation stability of the product during the storage period and reduce the risk that such oxidation products can potentially damage the normal physiological functions of the human body and promote the occurrence and development of diseases as much as possible, the anisidine value of the freshly processed polyunsaturated fatty acid oil is controlled to be as low as possible, which is one of the key indexes for measuring the quality of the fish oil.
Research shows that the polyunsaturated fatty ester has more double bonds in the molecular structure and is easily oxidized in an oxygen environment, so that the oxygen environment has great influence on the generation and the increase of the peroxide value of the polyunsaturated fatty acid. In addition to being affected by oxygen, the anisidine value of polyunsaturated fatty acids is also greatly affected by the increase in temperature, which increases rapidly during processing of the polyunsaturated fatty acids, particularly when high temperature processing steps are involved. The larger the number of double bonds in the polyunsaturated fatty acid molecule, the more significant the effect of oxygen and temperature on its peroxide value and anisidine value.
The peroxide number and anisidine number of polyunsaturated fatty acids inevitably increase during processing, so measures are generally taken to reduce these two indicators. The peroxide values are relatively easy to remove, but the anisidine values are more difficult to remove. The conventional methods for reducing the peroxide number and the anisidine number include a physical adsorption method, a chemical reaction method, or a combination of the two methods. The chemical method is to remove the micromolecular aldehyde and ketone after the reaction by utilizing the characteristic that the specific substance can react with the micromolecular aldehyde and ketone in the grease; the physical principle is that the micromolecular aldehyde ketone is removed after being adsorbed by porous substances such as active carbon, active clay, expansive soil, silica gel and the like. Both of these processes have their own advantages and disadvantages, such as the ability of the chemical process to reduce the anisidine value to a lower level, but the introduction of new chemicals which, if not effectively removed, would be impurities in the polyunsaturated fatty acids; the physical method is safer and easy to operate, but the prior process has a great defect that the adsorbent can adsorb a great amount of polyunsaturated fatty acid while adsorbing small molecular aldehyde ketone, so that the product loss is great, and the method is unacceptable for some products with higher added value, such as concentrated fish oil with high content.
CN103343048B relates to a method for reducing the anisidine value of high-content fish oil, which comprises adsorbing the fish oil with an adsorbent twice in an inert environment, wherein after the adsorption twice, the final anisidine value is reduced, but the loss of polyunsaturated fatty acid in the process can reach 47.6 percent at most.
CN108611190A also discloses a fish oil concentrate, the preparation method comprises removing anisidine value by using an adsorbent twice after urea inclusion, and the problem of excessive loss of effective components also exists.
CN101497026B discloses a decolorizing agent for reducing anisidine value of soybean oil for injection and a preparation method thereof, relating to the preparation of the decolorizing agent and having quite complicated process.
CN107746747A mentions a method for reducing peroxide value and anisidine value of polyunsaturated fatty acid oil, mainly adding a reducing agent, an adsorbent and an organic acid, and the method is a method combining a physical method and a chemical method.
CN106281725A discloses a method for reducing the content of DHA anisidine value by adding sodium hydroxide solution and diethyl malonate to polyunsaturated fatty acid oil to react, and introducing other organic substances into the polyunsaturated fatty acid oil.
CN105733818A describes a method for reducing the anisidine value of DHA grease, which mainly comprises the steps of adding concentrated phosphoric acid and a primary amine compound in sequence for reaction, and then carrying out high-pressure silica gel column chromatography, wherein the process is complex, and finally, more impurities are introduced into the product.
CN102976936B discloses a method for reducing peroxide value and anisidine value in unsaturated fatty acid ethyl ester, sodium borohydride and carbon-oxygen double bonds are used for generating reaction, so that aldehyde and ketone are converted into alcohol, the purpose of reducing peroxide value and anisidine value is achieved, and potential safety hazards exist in the reaction process.
In summary, in the above-mentioned method for reducing anisidine value, a chemical method brings a safety risk in production and introduces organic impurities into the final product, while a physical method is a simple method, but in the prior methods, there is a problem that the adsorbent takes away much polyunsaturated fatty acids and the product yield is low, and it is necessary to find a method for conveniently reducing anisidine value in polyunsaturated fatty acid oil with little loss of polyunsaturated fatty acids.
Disclosure of Invention
The invention mainly describes a method for reducing anisidine value in polyunsaturated fatty acid oil, and concretely relates to a method for reducing anisidine value in polyunsaturated fatty acid oil, which comprises the steps of dissolving the polyunsaturated fatty acid oil with an organic solvent in an inert gas environment, adding an adsorbent, stirring and adsorbing at a lower temperature, filtering the adsorbent, recovering the solvent, and obtaining the polyunsaturated fatty acid oil product with low anisidine value through molecular distillation or rectification.
Specifically, the method for reducing the anisidine value in the polyunsaturated fatty acid oil comprises the following steps: dissolving a polyunsaturated fatty acid raw material in an organic solvent; adding adsorbent, and stirring at lower temperature; filtering to remove the adsorbent, and blowing the liquid component in the adsorbent to dry by inert gas; 4) recovering the organic solvent in the filtrate to obtain a crude product; and 5) molecular distillation or rectification of the crude product to obtain the polyunsaturated fatty acid oil with low anisidine value.
"polyunsaturated fatty acids" in the description of the present invention refers to omega-3, omega-6 and omega-9 fatty acids having at least two C-C double bonds and their esters with glycerol or alkanols, preferably omega-3 fatty acids, including in particular fish oils (directly extracted omega-3 polyunsaturated fatty acids), algal oils (omega-3 polyunsaturated fatty acids of fermentation origin), linoleic acid, conjugated linoleic acid, linolenic acid, arachidonic acid and the like in varying amounts in one or more polyunsaturated fatty acid mixtures. In particular to polyunsaturated fatty acid fish oil.
The polyunsaturated fatty acid may be of the ethyl ester type or of the glyceride type. Preferably, the polyunsaturated fatty acid raw material adopted by the invention is triglyceride type polyunsaturated fatty acid fish oil raw material, ethyl ester type polyunsaturated fatty acid raw material, triglyceride type conjugated linoleic acid raw material, ethyl ester type arachidonic acid raw material, linolenic acid and linoleic acid mixture raw material. The total polyunsaturated fatty acid content in the polyunsaturated fatty acid raw material is 10-90 wt%.
Preferably, in step 1), the organic solvent mainly includes a solvent which is highly soluble in the polyunsaturated fatty acid and is easily volatilized, such as hexane, cyclohexane, petroleum ether, ethanol, ethyl acetate, and the like. The solvent is used in an amount of 10-500% (v/w) based on the amount of the polyunsaturated fatty acids. The adsorption temperature is 20-50 ℃.
Preferably, in step 2), the adsorbent added in the present invention mainly comprises activated carbon, activated clay, silica gel, diatomite, or a mixture thereof. The addition amount of the adsorbent is 0.5-10% (w/w) of the amount of the polyunsaturated fatty acid.
Preferably, after adsorption is complete, the adsorbent is removed by conventional means such as filtration or centrifugation, and the liquid component of the adsorbent is blown dry with an inert gas such as high purity nitrogen, argon, or carbon dioxide gas.
Preferably, after the adsorption is completed, the organic solvent is removed under vacuum to obtain the polyunsaturated fatty acid after the solvent is primarily removed.
Then, the polyunsaturated fatty acids are distilled or rectified. For ethyl ester type polyunsaturated fatty acid, removing light components containing micromolecular substances which are easy to generate peculiar smell under the conditions of 30-200Pa pressure and 80-130 ℃; then separating the positive part from the high boiling leftover material under the conditions of 5-30Pa pressure and 170-220 ℃. The obtained positive score is a high-content polyunsaturated fatty acid ethyl ester type product which is light in color, free from peculiar smell and low in peroxide value and anisidine value. Removing light components containing small molecular substances from glyceride type polyunsaturated fatty acid under 30-200Pa and 80-130 deg.C to obtain polyunsaturated fatty acid product with low odor, peroxide value and anisidine value.
The anisidine value is mainly determined according to a detection method of the anisidine value in the national standard GB/T24304-2009.
Distillation or rectification in the present invention is carried out using conventional short path molecular distillation or evaporation, thin film distillation or evaporation, falling film distillation or evaporation, continuous or discontinuous rectification or evaporation. The method is mainly used for separating different components by utilizing the boiling point difference among the components in a high vacuum environment at a certain temperature.
Compared with the prior art, the method for dissolving the polyunsaturated fatty acid oil by using the organic solvent before adding the adsorbent has the following advantages:
1) can effectively reduce the viscosity of the polyunsaturated fatty acid at lower temperature, is beneficial to the efficient adsorption of micromolecule substances such as aldehyde, ketone and the like which cause peroxide value and anisidine value by the adsorbent, and can reduce the dosage of the adsorbent. Since the peroxide number and anisidine number in polyunsaturated fatty acid oils tend to increase at higher temperatures and increase more markedly at higher temperatures, the operating temperature should be kept as low as possible during the operation of the polyunsaturated fatty acid oils, and in particular in the presence of trace amounts of oxygen, the polyunsaturated fatty acid oils are not allowed to reach temperatures of more than 50 ℃. However, at a lower temperature, the viscosity of the polyunsaturated fatty acid oil is increased, the higher the viscosity is, the slower the molecular movement is, so that the adsorption effect of the adsorbent on small molecular substances in the oil is deteriorated, and in the prior art, in order to achieve a good adsorption effect, the adsorption temperature is increased to be up to 100 ℃; or the dosage of the adsorbent is increased, the dosage of the adsorbent can be as high as 50% of the mass of the polyunsaturated fatty acid oil, on one hand, the adsorbent is wasted, a lot of solid wastes are generated, and great pressure is caused on environmental protection, on the other hand, in the adsorption process of the adsorbent, besides adsorbing small molecular impurities, the adsorbent can adsorb a certain active ingredient polyunsaturated fatty acid oil, the more the adsorbent is, the more the adsorbed active ingredient is, and great waste is caused, for example, in patents CN103343048B and CN108611190A, in order to achieve a good adsorption effect, the dosage of the adsorbent is generally between 5% and 20% of the polyunsaturated fatty acid oil, and the total dosage of the adsorbent can reach about 30% of the polyunsaturated fatty acid oil after two times of adsorption. The polyunsaturated fatty acid is firstly dispersed in the organic solvent, so that the viscosity of the system can be reduced, the adsorbent can effectively adsorb small molecular aldehydes and ketones at a lower temperature, the using amount of the adsorbent is greatly reduced, and a large amount of polyunsaturated fatty acid oil can not be adsorbed, so that the adsorption effect, the economic benefit and the environmental protection benefit are very favorable.
2) After the organic solvent is added, the adsorbent is easier to separate in the separation process of the adsorbent, and the adsorption loss of the polyunsaturated fatty acid is obviously reduced. In the prior art, because no organic solvent is added to reduce the viscosity of the system, the filtering or press filtering is difficult and slow in the separation process of the adsorbent, and the filter cake cannot be sufficiently pressed to dry, so that a large amount of polyunsaturated fatty acid is adsorbed in the adsorbent, waste is caused, sometimes about 50%, and the method is very uneconomical. In the invention, the viscosity of the system can be effectively reduced by adding the organic solvent into the system, the filtration is very easy and fast at a lower operation temperature, and after the filtration is finished, the filter cake is dried by inert gas until no liquid drops appear, so that the loss of polyunsaturated fatty acid is little, and the method is economically feasible.
The polyunsaturated fatty acid oil obtained as the final product has no peculiar smell, can well meet the requirements of consumers, the adsorbent applied or added in the production process can effectively reduce the peroxide value and anisidine value of the final product, and the adsorbent also has a certain removal effect on other trace substances in the product, such as color, heavy metals, dioxin, benzopyrene and the like.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are provided only for illustrating the technical solutions of the present invention and are not intended to limit the present invention.
Example 1
1500g of triglyceride type polyunsaturated fatty acid fish oil (specification: 5020TG) (50.2% of EPA, 20.8% of DHA, 77.4% of total polyunsaturated fatty acid content, peroxide value of 12.0, and anisidine value of 25.8, manufactured by Xinchang pharmaceutical factory, Zhejiang pharmaceutical Co., Ltd.) was added to 7500ml of absolute ethanol, and stirred and dissolved at 30 ℃. Adding 100g of activated clay and 50g of activated carbon, keeping at 30 deg.C, stirring and adsorbing for 1.0hr, filtering with adsorbent activated clay and activated carbon, filtering within 10min, and purging filter cake with high-purity nitrogen for 15min until no continuous liquid drop appears. And (4) recovering the solvent absolute ethyl alcohol in the filtrate in vacuum to obtain a crude fish oil product.
Removing light components from the crude fish oil product by primary molecular distillation at the temperature of 130 ℃ under the pressure of 200Pa to obtain 1408.5g of fish oil product with the peroxide value of 4.2 and the anisidine value of 7.4. 228g of a filter cake was recovered, and the adsorption loss was 4.8%.
Comparative example 2
Adding 1500g triglyceride type polyunsaturated fatty acid fish oil (EPA 50.2%, DHA 20.8%, total polyunsaturated fatty acid content 77.4%, peroxide value 12.0, anisidine value 25.8) into 100g activated clay and 50g activated carbon, stirring and adsorbing at 30 deg.C for 1.0hr, filtering with adsorbent activated clay and activated carbon at slow speed, and allowing a small amount of liquid drop to appear within 60 min.
Removing light components from the crude fish oil product by primary molecular distillation at the temperature of 130 ℃ under the pressure of 200Pa to obtain 1221.8g of fish oil product with the peroxide value of 9.1 and the anisidine value of 19.3. 421.2g of filter cake was recovered, and the adsorption loss was 18.08%.
Comparative example 3
1500g of triglyceride type polyunsaturated fatty acid fish oil raw material (EPA 50.2%, DHA 20.8%, total polyunsaturated fatty acid content 77.4%, peroxide value 12.0, anisidine value 25.8) was added to 7500ml of anhydrous ethanol, and dissolved at 30 ℃ with stirring. Adding 100g activated clay and 50g activated carbon, stirring and adsorbing at 30 deg.C for 1.0hr, filtering with adsorbent activated clay and activated carbon, and filtering within 11 min. And (4) recovering the solvent absolute ethyl alcohol in the filtrate in vacuum to obtain a crude fish oil product.
Removing light components from the crude fish oil product by primary molecular distillation at the temperature of 130 ℃ under the pressure of 200Pa to obtain 1360.4g of fish oil product with the peroxide value of 4.5 and the anisidine value of 8.1. 283.5g of filter cake was recovered, and the adsorption loss was 8.9%.
Comparative example 4
Adding 1500g triglyceride type polyunsaturated fatty acid fish oil (EPA 50.2%, DHA 20.8%, total polyunsaturated fatty acid content 77.4%, peroxide value 12.0, anisidine value 25.8) into 100g activated clay and 50g activated carbon, stirring and adsorbing at 130 deg.C for 1.0hr, filtering with adsorbent activated clay and activated carbon at slow speed, and allowing a small amount of liquid droplets to appear within 35 min.
Removing light components from the crude fish oil product by primary molecular distillation at the temperature of 130 ℃ under the pressure of 200Pa to obtain 1296.4g of fish oil product with the peroxide value of 7.6 and the anisidine value of 13.7. 337.1g of the cake was recovered, and the adsorption loss was 12.47%.
Comparing the technological processes of the four processes with the experimental results, it can be found that according to the process of the present invention, under the condition of adding the same amount of the adsorbent, the effect of removing peroxide value and anisidine value of the adsorbent can be improved by adding a certain amount of the organic solvent into the polyunsaturated fatty acid oil, the filtering speed is obviously accelerated, meanwhile, after the filtering is completed, most of the polyunsaturated fatty acid oil adsorbed in the adsorbent is purged by using the inert gas, the consumption of the polyunsaturated fatty acid oil caused by the adsorbent is reduced from nearly 20% to below 5%, if the inert gas purging step is not performed after the filtering is completed, the consumption of the polyunsaturated fatty acid oil reaches 8.9%, which indicates that the purging step is also necessary for improving the yield of the final product.
Example 5
600g of an ethyl ester type polyunsaturated fatty acid raw material (manufactured by Xinchang pharmaceutical factory, Zhejiang pharmaceutical Co., Ltd.; specification: 0525EE) (EPA 4.1%, DHA 25.2%, total polyunsaturated fatty acid content 30.8%, peroxide value 13.5, and anisidine value 37.9) obtained by fermentation was added with 60ml of hexane and dissolved at 20 ℃ with stirring. Adding 3g of activated carbon, stirring and adsorbing at 20 deg.C for 1.0hr, filtering with adsorbent activated carbon, and purging the filter cake with high purity carbon dioxide gas for 5min after filtering. And recovering the solvent ethane in the filtrate in vacuum to obtain crude algae oil.
And (3) performing thin-film distillation on the crude algal oil at the temperature of 80 ℃ under 30Pa to remove light components, raising the temperature to 170 ℃, and performing vacuum distillation under the pressure of 5Pa to obtain a positive component, namely 552g of ethyl ester algal oil, with the peroxide value of 7.1 and the anisidine value of 18.3. 4.7g of the filter cake was recovered, and the adsorption loss was 0.3%.
Example 6
1500g of a triglyceride type conjugated linoleic acid raw material (70 TG) (content: 70.5%, peroxide value: 12.1, anisidine value: 38.3, manufactured by Xinchang pharmaceutical factory, Zhejiang medical science Co., Ltd.) was added with 3000ml of ethyl acetate and dissolved at 50 ℃ with stirring. Adding 50g of activated carbon and 25g of diatomite, keeping at 50 ℃, stirring and adsorbing for 1.0hr, filtering the adsorbent activated carbon and the diatomite, completing the filtration within 7min, and purging the filter cake for 6min by using high-purity nitrogen after the filtration is completed until no continuous liquid drops appear. And recovering the solvent ethyl acetate in the filtrate in vacuum to obtain a crude product of the conjugated linoleic acid.
And (3) distilling the crude product of the conjugated linoleic acid at 50Pa and 120 ℃ by a falling film to remove light components to obtain 1397.2g of the product of the conjugated linoleic acid, wherein the peroxide value is 4.7 and the anisidine value is 12.4. 165.8g of a filter cake was recovered, and the adsorption loss was 6.1%.
Example 7
850g of ethyl ester type arachidonic acid (supplied from Xinchang pharmaceutical factory, Zhejiang pharmaceutical Co., Ltd.) (60.9% in content, deep red in color, strong in smell, 15.7 in peroxide value, 122.4 in anisidine value) was added to 850ml of cyclohexane, and the mixture was dissolved by stirring at 45 ℃. Adding 55g of activated carbon and 30g of silica gel, stirring and adsorbing at 45 ℃ for 1.0hr, filtering with adsorbent activated carbon and silica gel within 8min, and purging the filter cake with high-purity nitrogen for 6min after filtering till no continuous liquid drops appear. And recovering the solvent cyclohexane in the filtrate in vacuum to obtain a crude product of the arachidonic acid.
And (3) rectifying the crude arachidonic acid product at 30Pa and 120 ℃ to remove 168g of light components, raising the temperature to 220 ℃ and carrying out vacuum 15Pa to obtain 633g of normal ethyl ester type arachidonic acid oil, wherein the peroxide value of the product is 5.2 and the anisidine value is 17.3. 91.1g of the cake was recovered, and the adsorption loss was 6.4%.
Example 8
750g of a mixture of linolenic acid and linoleic acid (supplied by Xinchang pharmaceutical factory, Zhejiang pharmaceutical Co., Ltd.) (linolenic acid content: 37%, linoleic acid content: 52%, peroxide value: 8.3, and anisidine value: 27.9) was added to 300ml of petroleum ether, and the mixture was dissolved by stirring at 25 ℃. Adding 50g of activated carbon and 25g of diatomite, keeping the temperature at 25 ℃, stirring and adsorbing for 1.0hr, filtering the adsorbent activated carbon and the diatomite, finishing the filtering within 4min, and purging the filter cake for 3min by using high-purity argon after the filtering is finished until no continuous liquid drops appear. And recovering the solvent petroleum ether in the filtrate in vacuum to obtain crude products of linolenic acid and linoleic acid.
Removing 23.3g of light components from the mixture of the linolenic acid and the linoleic acid by a falling film distiller at the temperature of 120 ℃ under 180Pa to obtain 722.5g of linolenic acid and linoleic acid products, wherein the peroxide value of the products is 3.4, and the anisidine value is 10.2. 79.4g of the cake was recovered, and the adsorption loss was 5.8%.
It should be noted that the above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements may be made by those skilled in the art within the spirit and principles of the invention.
Claims (12)
1. A method for reducing anisidine value in polyunsaturated fatty acid oils comprising the steps of:
1) dissolving a polyunsaturated fatty acid raw material in an organic solvent;
2) adding adsorbent, stirring and adsorbing at lower temperature;
3) filtering to remove the adsorbent, and blowing the liquid component in the adsorbent to dry by inert gas;
4) recovering the organic solvent in the filtrate to obtain a crude product; and
5) after molecular distillation or rectification of the crude product, polyunsaturated fatty acid oil with low anisidine value is obtained.
2. The method of claim 1, wherein the polyunsaturated fatty acid is one or more of fish oil polyunsaturated fatty acid, algal oil, linoleic acid, conjugated linoleic acid, linolenic acid, and arachidonic acid.
3. The method of claim 1, wherein the polyunsaturated fatty acid feedstock has a total polyunsaturated fatty acid content of from 10 to 90 weight percent.
4. The method of claim 3, wherein the polyunsaturated fatty acids are in the triglyceride form or the ethyl ester form.
5. The method according to claim 1, wherein the organic solvent is used in an amount of 10 to 500% (v/w) based on the amount of the polyunsaturated fatty acid oil in step 1).
6. The method of claim 1 or 5, wherein the organic solvent is selected from hexane, cyclohexane, petroleum ether, ethanol, ethyl acetate.
7. The method of claim 1, wherein the adsorbent is added in an amount of 0.5-10% (w/w) of the amount of the polyunsaturated fatty acid in step 2).
8. The method of claim 1 or 7, wherein the adsorbent comprises activated carbon, activated clay, silica gel, diatomaceous earth, or a mixture thereof.
9. The method of claim 1, wherein in step 1), the dissolution temperature after the addition of the organic solvent is 20 to 50 ℃.
10. The method of claim 1, wherein in step 2), the adsorption temperature is 20-50 ℃ after the addition of the adsorbent.
11. The method of claim 1, wherein in step 3), the inert gas is nitrogen, argon, or carbon dioxide gas.
12. The method of claim 1, wherein in step 5), the molecular distillation or rectification comprises short path molecular distillation or evaporation, thin film distillation or evaporation, falling film distillation or evaporation, continuous or discontinuous rectification or evaporation.
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