CN109294735B - Ethyl ester type fish oil refining processing technology - Google Patents
Ethyl ester type fish oil refining processing technology Download PDFInfo
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- CN109294735B CN109294735B CN201811247001.0A CN201811247001A CN109294735B CN 109294735 B CN109294735 B CN 109294735B CN 201811247001 A CN201811247001 A CN 201811247001A CN 109294735 B CN109294735 B CN 109294735B
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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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- 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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Abstract
The invention relates to an ethyl ester type fish oil refining processing technology, which specifically comprises the following steps: s1, pretreatment of the hair fish oil: adding an adsorbent into the mao fish oil, stirring and adsorbing the mao fish oil by using a thermal magnetic stirrer, cooling the fish oil to room temperature after stirring for 30-40 min at a constant temperature, and filtering to remove the adsorbent for later use; s2, pre-esterification reaction: pumping the prepared fish oil into a reaction kettle, adding the uniformly mixed acid catalyst and ethanol into the reaction kettle, introducing condensed water and stirring, and under the condition of ethanol reflux, catalyzing the fish oil by the acid catalyst to perform pre-esterification reaction so as to reduce the acid value of the fish oil; s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method; and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
Description
Technical Field
The invention belongs to the technical field of food processing, and particularly relates to a refining processing technology of ethyl ester type fish oil.
Background
The fish oil is a general term of all oil substances in fish bodies and comprises body oil, liver oil, naphtha and the like, and the main fish oil is grease extracted from fatty fish, contains a large amount of unsaturated fatty acid and has health benefits of resisting inflammation, regulating blood fat and the like. The crude fish oil is also called as maotai oil, because the crude fish oil contains a certain amount of impurities such as water, impurities, colloid, fish body protein, free fatty acid and the like, the acid value is higher, the color is darker, and the coarse fish oil is accompanied by stronger fishy smell, the crude fish oil has use value after being refined and reaching certain quality indexes, and the commonly used refining process flow of the fish oil is as follows: crude fish oil-filtering-degumming-washing-drying-decolouring-winterizing-deodorizing-modulating. The fish oil thus obtained has low EPA and DHA content, and is generally required to be converted into fatty acid ethyl ester form, and then concentrated by molecular distillation or urea inclusion. The fish oil ethyl esterification method can be divided into an acid catalysis method, an alkali catalysis method, a lipase catalysis method and the like according to different catalysts. The traditional ethyl esterification process is to convert fish oil into fatty acid ethyl ester by transesterification reaction with ethanol under the catalysis of acid or alkali. The lipase catalysis method has the disadvantages of unsatisfactory ethylation degree and high catalyst cost, and industrial production cannot be realized. Compared with the acid ethyl esterification, the alkaline ethyl esterification of the fish oil has the advantages of high reaction speed, high yield, good product quality and the like, but the alkaline ethyl esterification is not suitable for the fish oil with higher acid value. During the alkaline-method ethylation reaction, the content of free fatty acid in the fish oil must be as low as possible (acid value is less than 1 mg/g), otherwise, saponification reaction between alkali and free fatty acid can affect esterification, separation of ethyl ester and soap is easy to cause difficulty, and the reaction yield is greatly reduced.
To solve the above problems, various methods have been developed to convert fish oil into a form of fatty acid ethyl ester.
Chinese patent publication No. 101796984a discloses a supercritical pressure-maintaining method for purifying deep sea fish oil, wherein supercritical carbon dioxide is used as an extractant and placed in an extraction tank to perform pressure-maintaining extraction to obtain refined ethyl ester type fish oil, and the supercritical extraction method has the disadvantages that the reaction needs to be performed at high temperature and high pressure, the equipment investment is expensive, the reaction conditions are harsh, fine control is required, and the production cost is high; chinese patent publication No. CN10567081A discloses a method for extracting decapterus maruadsi oil by low-temperature continuous phase change and decapterus maruadsi oil, which comprises compressing extractant into liquid, extracting decapterus maruadsi powder by an extraction device to obtain fish oil, converting the liquid extractant into gas, immediately compressing, converting into liquid, and extracting again by the extraction device.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the ethyl ester type fish oil refining processing technology, the fish oil is processed by adopting a two-step method combining pre-esterification and esterification, the yield of the fish oil and the quality of a product are improved, and the reaction process and the distillation concentration process are combined to carry out coupling operation by adopting a reactive distillation mode in the esterification process, so that the production period can be shortened, and the reaction speed is accelerated.
The technical scheme of the invention is as follows:
the ethyl ester type fish oil refining processing technology specifically comprises the following steps:
s1, pretreatment of the hair fish oil: adding an adsorbent into the crude fish oil, stirring and adsorbing the crude fish oil by using a thermomagnetic stirrer, keeping the vacuum degree at-0.2 to-1.0 MPa and the temperature at 68-72 ℃, stirring for 30-40 min, cooling the fish oil to room temperature, filtering to remove the adsorbent, and keeping the fish oil for later use;
s2, pre-esterification reaction: pumping the fish oil prepared in the step S1 into a reaction kettle, adding the uniformly mixed acid catalyst and ethanol into the reaction kettle, heating the mixed solution in the reaction kettle to 70-80 ℃, introducing condensed water and stirring, and under the condition that the ethanol flows back, catalyzing the fish oil by the acid catalyst for pre-esterification for 4-6 hours to react so as to reduce the acid value of the fish oil;
s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method;
and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
Wherein the adsorbent is one of activated clay, activated carbon or graphene.
Wherein the acid catalyst is a composite acid, an organic acid or SO which takes concentrated sulfuric acid as a main body4 2-/MxOyOne kind of solid super acid; the addition amount of the adsorbent is 3-5% of the total mass of the fish oil.
The composite acid mainly comprising concentrated sulfuric acid comprises 60-75 parts by weight of 98% concentrated sulfuric acid, 10-20 parts by weight of oxalic acid and 10-20 parts by weight of acetic acid; the organic acid is a mixture of methanesulfonic acid, p-toluenesulfonic acid and sulfamic acid; the SO4 2-/MxOyThe solid super acid is SO with acid strength less than-11.944 2-/ZrO2Solid superacids or SO4 2-/TiO2One of solid super acids.
Wherein, a nonionic surfactant is added in the pre-esterification reaction of the step S2 to increase the pre-esterification reaction rate; the non-ionic surfactant is one of polyethylene glycol, tween-60 or monoglyceride stearate.
Wherein 1.3-propanediol is added into the fish oil as a nutrient inhibitor before the esterification reaction in the step S3; the addition amount of the 1, 3-propylene glycol is 0.1-0.5% of the weight of the fish oil.
The reactive distillation method of the step S3 specifically comprises the following steps:
a1, feeding the fish oil and ethanol into a reactive distillation tower through a feed inlet respectively, feeding the fish oil and ethanol into an enzymatic catalytic reaction zone in the tower in a downward direction, carrying out fish oil ethylation reaction on the surface of an enzymatic catalyst, and gradually raising triglyceride, free fatty acid and volatile substances in the fish oil to a rectification section of the tower;
a2, allowing the fish oil passing through the enzymatic catalytic reaction zone to continuously flow downwards to enter the alkaline catalytic reaction zone, continuously performing fish oil ethylation reaction on the surface of an alkaline catalyst, allowing part of the final fish oil component to circulate and mix with the feed through reboiling gas at the bottom of the tower, returning the mixture to the tower, and allowing the other part of the final fish oil component to flow out of the tower bottom after heat exchange and cooling;
a3, carrying out rectification separation on triglyceride, free fatty acid and volatile substances in the fish oil at a rectification section of a tower, wherein the rectification separation temperature is 240-260 ℃, condensing and refluxing the triglyceride into the tower through a condenser, and removing the free fatty acid and the volatile substances.
Wherein the enzyme catalyst is microbial lipase or immobilized lipase; the alkaline catalyst selects sodium hydroxide or sodium bicarbonate as the catalyst according to the specific acid value of the fish oil catalyzed by the enzyme method.
Wherein the reflux ratio of the reactive distillation is 0.5-10.
Wherein, the step S4 of deoxidizing the fish oil by using the analytic deaerator specifically comprises the following steps:
b1, conveying the refined fish oil to be deoxygenated to an ejector through a deoxygenation pump, so that when the fish oil passes through the ejector at a certain flow rate, a certain negative pressure is formed, and oxygen-free gas is sucked in;
b2, fully mixing the fish oil and the oxygen-free gas in the mixing pipe, and then entering an analyzer, wherein oxygen dissolved in the fish oil is diffused into the oxygen-free gas in the analyzing system;
b3, introducing the gas with oxygen into a gas-liquid separator from the top of the decanter, introducing the gas from which the liquid is removed by the gas-liquid separator into a heat exchanger, heating to about 60-80 ℃, introducing the gas into a reactor, reacting with a reducing agent in the reactor, turning the gas into oxygen-free gas again, and introducing the oxygen-free gas into the next cycle, thereby achieving the purpose of continuously deoxidizing the fish oil.
The invention has the following beneficial effects:
1. the method adopts a two-step method combining pre-esterification and esterification to refine the fish oil. The crude oil generally contains high water content and free fatty acids, and if the raw oil is directly refined to remove the free fatty acids in the raw oil and then ester exchange is carried out, a lot of raw materials are lost; and the fish oil is refined by adopting a two-step method, so that the problems of overhigh ethanol consumption and overlong reaction time when acid catalysis is independently used are solved, the saponification problem caused by overhigh free fatty acid when alkali catalysis is independently used is also solved, in addition, the loss of raw materials can be reduced to a certain degree, the yield of fatty acid ethyl ester is increased, meanwhile, the reaction time is greatly shortened, and the fish oil yield is improved.
2. The pre-esterification reaction adopts composite acid, organic acid or solid super acid which takes concentrated sulfuric acid as a main catalyst to replace a pure concentrated sulfuric acid catalyst, the concentrated sulfuric acid has good catalytic effect, stable property and strong water absorption, but the concentrated sulfuric acid has serious corrosivity, is easy to carbonize and generate side reaction, and has scum after treatment.
3. The esterification reaction adopts the enzyme method and the alkaline method combined catalytic reaction, has the double advantages of the enzyme method catalysis and the alkaline method catalysis, firstly catalyzes the esterification reaction of the fish oil with high acid value and the ethanol by the lipase to reduce the acid value, and then catalyzes the esterification reaction of the fish oil by the alkaline method to improve the product yield and quality, thus the fish oil with high acid value and the fish oil with low acid value can realize higher reaction conversion rate by the combined catalytic reaction, avoid the defects of respective use, and be suitable for industrial production.
4. The invention adopts a reactive distillation tower to refine the fish oil after the pre-esterification reaction, the esterification reaction and the distillation concentration are integrated in one tower, the reaction section is arranged between the rectification section and the stripping section, the reactant is fed into a feed plate to react in the reaction section, and then the product is separated by the rectification section and the stripping section. Meanwhile, the thermodynamic efficiency of the fish oil esterification reaction system can be improved through reactive distillation, the ester exchange reaction is an exothermic reaction, and the reactive distillation tower can fully utilize the reaction heat to be directly used for distillation, so that the energy consumption of the system is greatly reduced.
5. According to the invention, 1, 3-propylene glycol is added into pre-esterified fish oil, unsaturated fatty acids DHA and EPA in the fish oil can be better fixed in the fish oil in the presence of the 1, 3-propylene glycol, and the DHA and EPA are inhibited from being released from subsequent process treatment, the inhibiting effect of the 1, 3-propylene glycol is due to the increase of intermolecular hydrogen bonds existing when the 1, 3-propylene glycol is used, and the linear geometry and the terminal arrangement of an alcohol functional group in the 1, 3-propylene glycol are considered to cause less steric hindrance effect and possibly provide more opportunities for forming intermolecular hydrogen bonds, more hydrogen bonds are formed among molecules, the quality of the original DHA and EPA is not influenced, and the release and loss of the DHA and EPA can be inhibited; and 1, 3-propanediol comprises less than 0.5% by weight of the fish oil, wherein the amount of 1, 3-propanediol is below the organoleptically perceptible taste threshold of the average consumer.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of the structure of the reactive distillation in the present invention.
Detailed Description
The invention will be further described with reference to preferred embodiments.
Example 1
The ethyl ester type fish oil refining processing technology specifically comprises the following steps:
s1, pretreatment of the hair fish oil: adding activated clay serving as an adsorbent into the crude fish oil, wherein the addition amount of the activated clay is 3% of the total mass of the fish oil, stirring and adsorbing the crude fish oil by using a thermomagnetic stirrer, cooling the fish oil to room temperature after stirring for 30min at the vacuum degree of-0.2 MPa and the temperature of 68 ℃, and filtering to remove the adsorbent for later use;
s2, pre-esterification reaction: pumping the fish oil prepared in the step S1 into a reaction kettle, and adding the uniformly mixed composite acid mainly containing concentrated sulfuric acid and ethanol into the reaction kettle; the composite acid mainly containing concentrated sulfuric acid comprises a mixture of 60 parts of concentrated sulfuric acid, 20 parts of oxalic acid and 20 parts of acetic acid, wherein the mass fraction of the mixture is 98%; heating the mixed solution in the reaction kettle to 70 ℃, introducing condensed water and stirring, and catalyzing the fish oil to perform pre-esterification reaction for 4 hours by using an acid catalyst under the condition of ethanol reflux so as to reduce the acid value of the fish oil; polyethylene glycol can be added in the pre-esterification reaction, and the addition of the nonionic surfactant is helpful for promoting the mutual solubility of two phases, so that the pre-esterification reaction rate is increased, and the effect of improving the catalytic pre-esterification reaction effect of the catalyst can be achieved;
s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method;
and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
Wherein 1.3-propanediol is added into the fish oil as a release inhibitor of the nutrient components DHA and EPA before the esterification reaction in the step S3; the addition amount of the 1, 3-propylene glycol is 0.1 percent of the weight of the fish oil.
Example 2
The ethyl ester type fish oil refining processing technology is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, pretreatment of the hair fish oil: adding activated carbon as adsorbent into the crude fish oil, wherein the addition amount of the activated carbon is 5% of the total mass of the crude fish oil, stirring and adsorbing the crude fish oil by using a thermomagnetic stirrer, cooling the crude fish oil to room temperature after stirring for 40min at the vacuum degree of-1.0 MPa and the temperature of 72 ℃, and filtering to remove the adsorbent for later use;
s2, pre-esterification reaction: pumping the fish oil prepared in the step S1 into a reaction kettle, and adding the organic acid and the ethanol which are uniformly mixed into the reaction kettle; the organic acid is a mixture of methanesulfonic acid, p-toluenesulfonic acid and sulfamic acid; heating the mixed solution in the reaction kettle to 80 ℃, introducing condensed water and stirring, and catalyzing the fish oil to perform pre-esterification reaction for 6 hours by using an acid catalyst under the condition of ethanol reflux so as to reduce the acid value of the fish oil; tween-60 can be added in the pre-esterification reaction, and the addition of the nonionic surfactant is helpful for promoting the mutual solubility of two phases, so that the pre-esterification reaction rate is increased, and the effect of improving the catalytic pre-esterification reaction effect of the catalyst can be achieved;
s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method;
and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
Wherein 1.3-propanediol is added into the fish oil as a release inhibitor of the nutrient components DHA and EPA before the esterification reaction in the step S3; the addition amount of the 1, 3-propylene glycol is 0.5 percent of the weight of the fish oil.
Example 3
The ethyl ester type fish oil refining processing technology is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, pretreatment of the hair fish oil: adding graphene serving as an adsorbent into the crude fish oil, wherein the addition amount of the graphene is 5% of the total mass of the fish oil, stirring and adsorbing the crude fish oil by using a thermal magnetic stirrer, cooling the fish oil to room temperature after stirring at the vacuum degree of-0.6 MPa and the temperature of 70 ℃ for 35min, and filtering to remove the adsorbent for later use;
s2, pre-esterification reaction: pumping the fish oil prepared in the step S1 into a reaction kettle, and adding the evenly mixed SO into the reaction kettle4 2-/MxOySolid super acid and ethanol; the SO4 2-/MxOyType solid superacid is SO4 2-/ZrO2Solid superacids or SO4 2-/TiO2One of the solid super acids, the acid strength is less than-11.94; heating the mixed solution in the reaction kettle to 75 ℃, introducing condensed water and stirring, and catalyzing the fish oil to perform pre-esterification reaction for 5 hours by using an acid catalyst under the condition of ethanol reflux so as to reduce the acid value of the fish oil; the stearic acid monoglyceride can be added in the pre-esterification reaction, and the addition of the nonionic surfactant is helpful for promoting the mutual solubility of two phases, so that the pre-esterification reaction rate is increased, and the effect of improving the catalytic pre-esterification reaction effect of the catalyst can be achieved;
s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method;
and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
Wherein 1.3-propanediol is added into the fish oil as a release inhibitor of the nutrient components DHA and EPA before the esterification reaction in the step S3; the addition amount of the 1, 3-propylene glycol is 0.3 percent of the weight of the fish oil.
The reactive distillation method of step S3 of examples 1-3 above, specifically including the following:
a1, allowing fish oil and ethanol to enter a reactive distillation tower through a feed inlet respectively, allowing the fish oil and ethanol to enter an enzymatic catalytic reaction zone in the tower in a downward manner, and performing fish oil ethylation reaction on the surface of an enzymatic catalyst; the enzyme method catalyst is microbial lipase or immobilized lipase; the triglyceride, free fatty acid and volatile substances in the fish oil gradually rise to the rectifying section of the tower;
a2, continuously allowing the fish oil passing through the enzymatic catalytic reaction zone to continuously flow downwards into the alkaline catalytic reaction zone, and continuously performing fish oil ethylation reaction on the surface of the alkaline catalyst; the alkaline catalyst selects sodium hydroxide or sodium bicarbonate as a catalyst according to the specific acid value of the fish oil catalyzed by the enzyme method; finally, returning the fish oil component into the tower after a part of reboiling gas at the tower bottom is circulated and mixed with the feed, and collecting the other part of the reboiling gas after heat exchange and cooling through the tower bottom;
a3, carrying out rectification separation on triglyceride, free fatty acid and volatile substances in the fish oil at a rectification section of a tower, wherein the rectification separation temperature is 240-260 ℃, condensing and refluxing the triglyceride into the tower through a condenser, and removing the free fatty acid and the volatile substances.
Wherein the reflux ratio of the reactive distillation is 0.5-10.
In step S4 of the above embodiments 1 to 3, the method for removing oxygen from fish oil by using an analytic oxygen remover specifically includes the following steps:
b1, conveying the refined fish oil to be deoxygenated to an ejector through a deoxygenation pump, so that when the fish oil passes through the ejector at a certain flow rate, a certain negative pressure is formed, and oxygen-free gas is sucked in;
b2, fully mixing the fish oil and the oxygen-free gas in the mixing pipe, and then entering an analyzer, wherein oxygen dissolved in the fish oil is diffused into the oxygen-free gas in the analyzing system;
b3, introducing the gas with oxygen into a gas-liquid separator from the top of the decanter, introducing the gas from which the liquid is removed by the gas-liquid separator into a heat exchanger, heating to about 60-80 ℃, introducing the gas into a reactor, reacting with a reducing agent in the reactor, turning the gas into oxygen-free gas again, and introducing the oxygen-free gas into the next cycle, thereby achieving the purpose of continuously deoxidizing the fish oil.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The ethyl ester type fish oil refining processing technology is characterized by comprising the following steps:
s1, pretreatment of the hair fish oil: adding an adsorbent into the crude fish oil, stirring and adsorbing the crude fish oil by using a thermal magnetic stirrer, keeping the vacuum degree of-0.2 to-1.0 MPa and the temperature of 68 to 72 ℃, stirring for 30 to 40min, cooling the fish oil to room temperature, filtering to remove the adsorbent, and keeping the fish oil for later use;
s2, pre-esterification reaction: pumping the fish oil prepared in the step S1 into a reaction kettle, adding the uniformly mixed acid catalyst and ethanol into the reaction kettle, heating the mixed solution in the reaction kettle to 70-80 ℃, introducing condensed water and stirring, and under the condition that the ethanol flows back, catalyzing the fish oil by the acid catalyst to perform pre-esterification reaction for 4-6 hours so as to reduce the acid value of the fish oil; the acid catalyst is a composite acid, an organic acid or SO taking concentrated sulfuric acid as a main body4 2-/MxOyOne kind of solid super acid;
s3, esterification: pumping the fish oil prepared by the pre-esterification reaction in the step S2 into a reactive distillation tower for reaction, and synchronously performing esterification reaction and distillation concentration of fish oil refining in the reactive distillation tower; the esterification reaction is a combined catalytic reaction of an enzyme method and an alkaline method;
and S4, freezing and decoloring the fish oil prepared by the esterification reaction in the step S3, and deoxidizing to obtain the ethyl ester type fish oil.
2. The ethyl ester type fish oil refining process according to claim 1, characterized in that: the adsorbent is one of activated clay, activated carbon or graphene; the addition amount of the adsorbent is 3-5% of the total mass of the fish oil.
3. The ethyl ester type fish oil refining process according to claim 1, characterized in that: the composite acid mainly containing concentrated sulfuric acid comprises 60-80 parts by weight of concentrated sulfuric acid with the mass fraction of 98%,10-20 parts of oxalic acid and 10-20 parts of acetic acid; the organic acid is a mixture of methanesulfonic acid, p-toluenesulfonic acid and sulfamic acid; the SO4 2-/MxOyThe solid super acid is SO with acid strength less than-11.944 2-/ZrO2Solid superacids or SO4 2-/TiO2One of solid super acids.
4. The ethyl ester type fish oil refining process according to claim 1, characterized in that: adding a nonionic surfactant to the pre-esterification reaction of step S2 to increase the pre-esterification reaction rate; the non-ionic surfactant is one of polyethylene glycol, tween-60 or monoglyceride stearate.
5. The ethyl ester type fish oil refining process according to claim 1, characterized in that: adding 1, 3-propanediol into the fish oil as a nutrient inhibitor before the esterification reaction in the step S3; the addition amount of the 1, 3-propylene glycol is 0.1-0.5% of the weight of the fish oil.
6. The ethyl ester type fish oil refining process according to claim 1, characterized in that: the reactive distillation method of the step S3 specifically comprises the following steps:
a1, feeding the fish oil and ethanol into a reactive distillation tower through a feed inlet respectively, feeding the fish oil and ethanol into an enzymatic catalytic reaction zone in the tower in a downward direction, carrying out fish oil ethylation reaction on the surface of an enzymatic catalyst, and gradually raising triglyceride, free fatty acid and volatile substances in the fish oil to a rectification section of the tower;
a2, allowing the fish oil passing through the enzymatic catalytic reaction zone to continuously flow downwards to enter the alkaline catalytic reaction zone, continuously performing fish oil ethylation reaction on the surface of an alkaline catalyst, allowing part of the final fish oil component to circulate and mix with the feed through reboiling gas at the bottom of the tower, returning the mixture to the tower, and allowing the other part of the final fish oil component to flow out of the tower bottom after heat exchange and cooling;
a3, carrying out rectification separation on triglyceride, free fatty acid and volatile substances in the fish oil at a rectification section of a tower, wherein the rectification separation temperature is 240-260 ℃, condensing and refluxing the triglyceride into the tower through a condenser, and removing the free fatty acid and the volatile substances.
7. The ethyl ester type fish oil refining process according to claim 6, characterized in that: the enzyme method catalyst is microbial lipase or immobilized lipase; the alkaline catalyst selects sodium hydroxide or sodium bicarbonate as the catalyst according to the specific acid value of the fish oil catalyzed by the enzyme method.
8. The ethyl ester type fish oil refining process according to claim 7, characterized in that: the reflux ratio of the reactive distillation is 0.5-10.
9. The ethyl ester type fish oil refining process according to claim 1, characterized in that: in the step S4, the fish oil is deoxygenated by using an analytic deoxygenator, specifically comprising the following steps:
b1, conveying the refined fish oil to be deoxygenated to an ejector through a deoxygenation pump, so that when the fish oil passes through the ejector at a certain flow rate, a certain negative pressure is formed, and oxygen-free gas is sucked in;
b2, fully mixing the fish oil and the oxygen-free gas in the mixing pipe, and then entering an analyzer, wherein oxygen dissolved in the fish oil is diffused into the oxygen-free gas in the analyzing system;
b3, introducing the gas with oxygen into a gas-liquid separator from the top of the decanter, introducing the gas from which the liquid is removed by the gas-liquid separator into a heat exchanger, heating to about 60-80 ℃, introducing the gas into a reactor, reacting with a reducing agent in the reactor, turning the gas into oxygen-free gas again, and introducing the oxygen-free gas into the next cycle, thereby achieving the purpose of continuously deoxidizing the fish oil.
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| CN111943837B (en) * | 2020-07-23 | 2022-07-15 | 浙江省海洋开发研究院 | Process for preparing high-purity EPA or DHA ethyl ester by combining molecular distillation with dynamic axial chromatography |
| CN115154486B (en) * | 2022-07-07 | 2023-11-21 | 四川欣美加生物医药有限公司 | Method for reducing content of oligomer in fish oil |
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| CN101824364B (en) * | 2010-04-09 | 2012-08-22 | 浙江兴业集团有限公司 | Method for deacidifying and refining high-acid value fish oil by using enzyme method |
| CN102911795A (en) * | 2012-11-26 | 2013-02-06 | 天津大学 | Method for preparing fish oil ethyl ester by microwave esterification and purifying ethyl eicosapentaenoate |
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