CN106753817A - A kind of industrialized preparing process of highly unsaturated fatty acid fish oil - Google Patents

Abstract

The present invention relates to a kind of industrialized preparing process of highly unsaturated fatty acid fish oil, comprise the following steps：(1) triglyceride type fish oil, ethanol and acid are carried out into ester exchange reaction；(2) product of transesterification reaction that step (1) is obtained is carried out into multiple-grade molecular distillation；(3) product obtained after step (2) is distilled carries out freezing decolouring, deoxygenation, obtains ethyl ester type fish oil.Present invention process is simple, can produce the exquisite fish oil of EPA+DHA contents (30 80) %, can require customization EPA+DHA different contents according to different, and the product of EPA, DHA different proportion obtains preferably economic benefit.

Description

A kind of industrial production method of highly unsaturated fatty acid fish oil

technical field

The invention relates to a preparation method of fish oil, in particular to a method of combining esterification, distillation, decolorization and membrane treatment to prepare a highly unsaturated fatty acid ethyl ester type fish oil, which belongs to the technical field of fish oil production.

Background technique

Fish oil is rich in Omega-3 unsaturated fatty acids, and its main components EPA and DHA have the functions of preventing cardiovascular disease, lowering cholesterol, reducing thrombosis, promoting blood circulation, preventing cardiovascular and cerebrovascular diseases, reducing arteriosclerosis, lowering fat and blood pressure, eliminating Fatigue, relieve gout and rheumatoid arthritis, promote eye development, etc. In addition, EPA and DHA are also important components of brain nerve cells and human defense system, which can enhance the function of the nervous system, improve intelligence and brain, and prevent Alzheimer's disease and other effects.

There are three forms of unsaturated fatty acids in fish oil: triglyceride type, ethyl ester type and methyl ester type. Methyl ester type fish oil is produced by the reaction of fish oil and methanol, and improper operation will cause safety hazards; comparison of molecular weight of triglyceride type fish oil Large, relatively stable, not easy to decompose or volatilize, so it is not conducive to increasing the content of EPA and DHA; compared with triglyceride fish oil, ethyl ester fish oil has a smaller molecular weight, good heat sensitivity, and is easy to oxidize and decompose, which is conducive to increasing the content of EPA and DHA.

Chinese patent documents CN103509651A and CN1072711C have introduced the method of obtaining ethyl ester type fish oil with alkali catalysis, but using alkali catalysis not only causes grease loss, reduces transesterification conversion rate, and the recycling process of free fatty acid can cause very serious environmental pollution, production higher cost.

Chinese patent document CN105087158A introduces a method for reducing the acid value in the refining process of ethyl ester type fish oil, which adopts secondary esterification. However, this method not only increases the consumption of auxiliary materials, but also increases the consumption of reaction time and steam, which is unfavorable for cost control.

Chinese patent document CN105779140A discloses a preparation method of high-content EPA ethyl ester type fish oil, using crude fish oil as raw material, first carrying out alcoholysis reaction with 1,3-specific lipase, and separating glyceride and ethyl ester by vacuum short-path distillation. The obtained ethyl ester fish oil is obtained through rectification and urea clathrate to obtain more than 80% EPA ethyl ester fish oil, and the total omega-3 fatty acid content is more than 90%. However, this method adopts lipase to carry out alcoholysis reaction, and the cost is relatively high, and this enzyme is to specifically act on EPA, obtains high-content EPA ethyl ester type fish oil.

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides an industrial production method of highly unsaturated fatty acid fish oil. The process of the invention is simple, and the ethyl ester fish oil is preliminarily obtained through an acid-catalyzed glyceride fish oil and absolute ethanol through one transesterification, and then through distillation, freezing decolorization, oxygen removal, and membrane refining, the EPA+DHA content can be produced at 30-80%. The refined fish oil can be customized according to the requirements of different EPA+DHA content, EPA, DHA different ratio products, to achieve better economic benefits.

Technical scheme of the present invention is as follows:

A method for industrialized production of highly unsaturated fatty acid fish oil, comprising the following steps:

(1) carrying out transesterification reaction with triglyceride type fish oil, ethanol and acid;

(2) the transesterification product obtained in step (1) is carried out to multistage molecular distillation;

(3) The product obtained after the distillation in step (2) is subjected to freeze decolorization and oxygen removal to obtain ethyl ester fish oil.

According to the present invention, preferably, the EPA+DHA content of triglyceride type fish oil in step (1) is (10-40)%, mass percent;

Preferably, before the transesterification reaction, the triglyceride-type fish oil is first dehydrated (0.5-5) h at a vacuum degree of - (0.2-1.0) MPa and a temperature of (90-120) °C;

Preferably, the ethanol is one of absolute ethanol, 95v% ethanol or 75v% ethanol; the acid is one of concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid, further preferably, the concentration of concentrated sulfuric acid is (70-98) wt%, concentrated hydrochloric acid concentration is (35-38) wt%, concentrated nitric acid concentration is (60-69) wt%;

Preferably, the added amount of ethanol is (10-60)% of the weight of triglyceride fish oil, the added amount of acid is (1-10)% of the weight of triglyceride fish oil, and the reaction temperature is (60-60)%. 100)°C, the reaction time is (10-40)h.

According to the present invention, preferably, the distillation in step (2) adopts multi-stage molecular distillation to obtain different contents of EPA and DHA components, and the distillation temperature range is (80-190) ° C;

Further preferably, 3-5 grades of molecular distillation are used; first-stage distillation vacuum degree-(5-20) Pa, temperature (80-110) ° C; secondary distillation vacuum degree-(2-15) Pa, temperature (90- 160) ℃; three-stage distillation vacuum - (2-10) Pa, temperature (90-180) ℃; four-stage distillation vacuum - (2-10) Pa, temperature (90-180) ℃; five-stage distillation vacuum Degree - (2-10) Pa, temperature (100-190) ° C.

According to the present invention, preferably, the freezing described in step (3) is to carry out the product after distillation at a temperature of - (5-40) °C; the decolorization is carried out by adding triglyceride type fish oil (2-20) % mass of activated carbon for decolorization, further preferably in a decolorization kettle, the decolorization process needs to pass into the refrigerant water as a circulating medium, so that the temperature of the decolorization kettle is controlled at - (5-40) ° C, and the decolorization time is (0.5-5) h .

According to the present invention, preferably, after the decolorization in step (3), the refined ethyl ester type fish oil is obtained by plate and frame filtration and membrane filtration;

Preferably, the membrane is one of microfiltration membrane (MF), ultrafiltration membrane (μF), nanofiltration membrane (NF) or reverse osmosis membrane (RO), and the pressure before and after the membrane is (0.02-2) MPa ;

Preferably, the plate and frame filtration pressure is (0.5-2) MPa, and the plate and frame filter medium is one of diatomite, perlite, cellulose or charcoal powder;

Preferably, nitrogen gas (1-10) min is passed through during plate and frame filtration and membrane filtration;

Preferably, the oxygen removal process is nitrogen gas removal. The obtained refined ethyl ester type fish oil is respectively filled with nitrogen (1-10) min before and after loading into the finished barrel.

The beneficial effects of the present invention are as follows:

1. The present invention adopts one-time esterification, which not only saves time, but also saves the amount of auxiliary materials and reduces energy consumption.

2. The present invention adopts multi-stage molecular distillation, and fish oil with different EPA+DHA contents can be customized according to different needs.

3. Membrane treatment can effectively remove heavy metals such as microorganisms, lead, tribute, and arsenic in fish oil, and the product quality is higher.

detailed description

In order to make the features and advantages of the present invention more obvious and understandable, the invention will be further described in detail below in conjunction with examples, so that those skilled in the art can better understand the present invention, but the protection scope required by the present invention is not limited to Examples describe the range.

Example 1

Add 2000kg (EPA+DHA) fish oil with a mass content of 20% triglyceride in the transesterification reaction kettle, dehydrate at a vacuum degree of -0.08MPa and a temperature of 100°C for 3h, add 400kg of absolute ethanol, and 40kg of 98wt% Concentrated sulfuric acid, react at 80°C for 10h, and the esterified oil obtained after the reaction is distilled through a five-stage molecular distillation tower. Vacuum degree - (2-15) Pa, temperature (90-130) ° C, three-stage distillation tower vacuum degree - (2-10) Pa, temperature (90-130) ° C, four-stage distillation tower vacuum degree - (2- 10) Pa, temperature (90-130) ° C, vacuum degree of five-stage distillation tower - (2-10) Pa, temperature (100-180) ° C, the required components obtained after distillation are placed in a -15 ° C freezer, Add 6% activated carbon of fish oil quality to decolorize for 1.5h, then add diatomaceous earth to carry out plate and frame filtration, the obtained filtrate is refined through microfiltration membrane, filled with nitrogen and deoxygenated for finished product packaging.

Example 2

Add 2000kg (EPA+DHA) fish oil with a mass content of 25% triglyceride to the transesterification reactor, dehydrate it for 4 hours at a vacuum degree of -0.08MPa and a temperature of 100°C, add 500kg of absolute ethanol, and 50kg of 98wt% concentrated sulfuric acid , reacted at 80°C for 8h, and the esterified oil obtained after the reaction was distilled through a five-stage molecular distillation tower, the vacuum degree of the first-stage distillation tower was - (5-20) Pa, the temperature was (80-110)°C, and the vacuum degree of the second-stage distillation tower was -(2-15)Pa, temperature (90-130)℃, vacuum degree of the three-stage distillation tower-(2-10)Pa, temperature (90-130)℃, vacuum degree of the fourth-stage distillation tower-(2-10) Pa, temperature (90-130) ° C, vacuum degree of five-stage distillation tower - (2-10) Pa, temperature (100-180) ° C, put the required components obtained after distillation in a -20 ° C freezer, add fish oil 7% of the mass of activated carbon is decolorized for 1 hour, and then diatomaceous earth is added for plate and frame filtration, and the obtained filtrate is refined through a nanofiltration membrane, filled with nitrogen and deoxygenated, and packaged as a finished product.

Example 3

Add 2000kg (EPA+DHA) fish oil with a mass content of 30% triglyceride to the transesterification reactor, dehydrate it for 4 hours at a vacuum degree of -0.08MPa and a temperature of 100°C, add 600kg of absolute ethanol, and 60kg of 98wt% concentrated sulfuric acid , reacted at 80°C for 6h, and the esterified oil obtained after the reaction was distilled through a five-stage molecular distillation tower, the vacuum degree of the first-stage distillation tower was - (5-20) Pa, the temperature was (80-110)°C, and the vacuum degree of the second-stage distillation tower was -(2-15) Pa, temperature (90-130) °C, vacuum degree of the three-stage distillation tower - (2-10) Pa, temperature (90-130) °C, vacuum degree of the fourth-stage distillation tower - (2-10) Pa, temperature (90-130) ° C, vacuum degree of five-stage distillation tower - (2-10) Pa, temperature (100-180) ° C, put the required components obtained after distillation in a -25 ° C freezer, add fish oil 5% of the mass of activated carbon is decolorized for 2 hours, and then perlite is added for plate and frame filtration, and the obtained filtrate is refined through an ultrafiltration membrane, filled with nitrogen and deoxygenated for finished product packaging.

Test case

The fish oil that embodiment 1-3 makes is measured EPA, DHA content, as shown in table 1.

Table 1 each embodiment gained fish oil EPA, DHA content

serial number EPA content (%) DHA content (%) Example 1 18.5 12.4 Example 2 36.3 24.6 Example 3 50.6 25.3

It can be seen from the comparison in Table 1 that fish oils with different EPA and DHA contents can be obtained under different conditions.

Claims (10)

1. a method for industrialized production of highly unsaturated fatty acid fish oil, comprising the following steps: (1) carrying out transesterification reaction with triglyceride type fish oil, ethanol and acid; (2) the transesterification product obtained in step (1) is carried out to multistage molecular distillation; (3) The product obtained after the distillation in step (2) is subjected to freeze decolorization and oxygen removal to obtain ethyl ester fish oil. 2. the industrialized production method of highly unsaturated fatty acid fish oil according to claim 1, is characterized in that, the EPA+DHA content of triglyceride type fish oil in step (1) is (10-40)%, mass percent. 3. the industrialized production method of highly unsaturated fatty acid fish oil according to claim 1, is characterized in that, before the transesterification reaction in step (1), earlier triglyceride type fish oil is-(0.2-1.0) MPa, dehydration (0.5-5) h at a temperature of (90-120) ° C; Preferably, the ethanol is one of absolute ethanol, 95v% ethanol or 75v% ethanol; the acid is one of concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid. 4. the industrial production method of highly unsaturated fatty acid fish oil according to claim 1, is characterized in that, the addition of ethanol described in step (1) is (10-60)% of triglyceride type fish oil weight, The addition amount of acid is (1-10)% of triglyceride type fish oil weight; Preferably, the reaction temperature is (60-100)°C, and the reaction time is (10-40)h. 5. the industrialized production method of highly unsaturated fatty acid fish oil according to claim 1 is characterized in that, the distillation in step (2) adopts multistage molecular distillation to obtain the EPA and the DHA component of different contents, and the distillation temperature range is ( 80-190) ℃; Preferably, 3-5 stages of molecular distillation are used; the vacuum degree of the primary distillation is - (5-20) Pa, the temperature is (80-110) °C; the vacuum degree of the secondary distillation is - (2-15) Pa, the temperature is (90-160) )°C; three-stage distillation vacuum - (2-10) Pa, temperature (90-180) ° C; four-stage distillation vacuum - (2-10) Pa, temperature (90-180) ° C; five-stage distillation vacuum -(2-10)Pa, temperature (100-190)℃. 6. the industrial production method of highly unsaturated fatty acid fish oil according to claim 1, is characterized in that, the freezing described in step (3) is that the product after distillation is carried out at-(5-40) ℃ of temperature; The decolorization is carried out by adding triglyceride type fish oil (2-20)% mass active carbon for decolorization. 7. the industrialized production method of highly unsaturated fatty acid fish oil according to claim 1 is characterized in that, after decolorization finishes in step (3), by plate and frame filtration and membrane filtration, obtains refined ethyl ester type fish oil. 8. the industrial production method of highly unsaturated fatty acid fish oil according to claim 7, is characterized in that, the membrane described in step (3) is microfiltration membrane (MF), ultrafiltration membrane (μF), nanofiltration membrane One of (NF) or reverse osmosis membrane (RO), the pressure before and after the membrane is (0.02-2) MPa. 9. the industrial production method of highly unsaturated fatty acid fish oil according to claim 7, is characterized in that, the plate and frame filtration pressure described in step (3) is (0.5-2) MPa, and the plate and frame filter medium is diatom One of earth, perlite, cellulose or charcoal powder. 10. the industrial production method of highly unsaturated fatty acid fish oil according to claim 1, is characterized in that, the deoxygenation process described in step (3) is logical nitrogen deoxygenation.