CN1084380C - Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil - Google Patents
Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil Download PDFInfo
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- CN1084380C CN1084380C CN99114410A CN99114410A CN1084380C CN 1084380 C CN1084380 C CN 1084380C CN 99114410 A CN99114410 A CN 99114410A CN 99114410 A CN99114410 A CN 99114410A CN 1084380 C CN1084380 C CN 1084380C
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- fish oil
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Abstract
The present invention relates to a process for preparing fish oil which is rich in polyenoic acid ethyl ester from crude fish oil. The process comprises the steps: carrying out ester exchange reaction directly between crude fish oil and absolute alcohol under the catalysis of an acid catalyst to obtain crude fish oil ethyl ester; processing the ethyl ester by a urea covering process, and then decoloring the ethyl ester to obtain rough fish oil which is rich in eicosapentaenoic acid ethyl ester (EPA-E) and docosahexenoic acid ethyl ester (DHA-E). The process does not need the traditional complex steps of deacidification, deodorization, decolorization, etc. so as to simplify preparation steps, save raw materials, enhance the quality of products and basically eliminate the severe contamination to the environment.
Description
The present invention relates to a kind of novel method of producing fish oil ethyl ester, belong to the technical field of their ester class of oil and fat preparation with the direct transesterify of crude fish oil.
Make high density (timnodonic acid and docosahexenoic acid) ethyl ester (EPA-E+DHA-E) with crude fish oil, general method comprises following process: the depickling of crude fish oil elder generation, deodorization, decolouring, esterification then, urine bag and refining.The shortcoming of this method is that process is numerous and diverse, crude fish oil loss big (about 25～30%), environment is caused serious pollution, the smell severe contamination ambient air of discharging during as deodorization, reclaim though 25～30% organism of loss part is made tankage, contain dirty waste water environmental pollution and cause serious threat.If will handle, then expense is difficult to bear.
The objective of the invention is to improve the production method of fish oil ethyl esterization, crude fish oil in the presence of an acidic catalyst, is directly carried out transesterification reaction with dehydrated alcohol, obtain the crude fish oil ethyl ester.After the processing of urine bag, activated carbon decolorizing are made with extra care, obtain the refined fish oil of high polyenoic acid ethyl ester content then.
The objective of the invention is to realize with following technical proposals:
The present invention is a kind of method of producing the high polyenoic acid ethyl ester content refined fish oil from crude fish oil.It is characterized in that, with crude fish oil in the presence of an acidic catalyst, with excessive dehydrated alcohol; under 30～85 ℃, nitrogen protection; carry out transesterification reaction, the weight of material ratio of reaction is: crude fish oil: dehydrated alcohol: acid is 1: 0.9～1.8: 0.03～0.10, and reaction finishes; after boiling off dehydrated alcohol; raffinate washes with water once, uses (1～5) % phosphoric acid solution to wash once again, washes with water at last to neutrality; branch vibration layer gets the crude fish oil ethyl ester.Then ethanol and urea are added in the reactor; under nitrogen protection; stir; after being heated to the urea dissolving; add above-mentioned crude fish oil ethyl ester, crude fish oil ethyl ester: ethanol: the weight of material ratio of urea is 1: 3～4.5: 2.1～2.5, continues insulation after 10～30 minutes; be chilled to room temperature, elimination urine bag thing.After the filtrate washing, divide and remove alcohol-water layer.The oil reservoir solvent cut.Add activated carbon decolorizing, the filtering gac boils off solvent, gets the refined fish oil that faint yellow height contains EPA-EE and docosahexenoic acid ethyl ester.Measure content, acidity and peroxide value.
An acidic catalyst of transesterify is meant the vitriol oil, hydrogenchloride or phosphoric acid, the preferably vitriol oil.Dilution is meant sherwood oil or hexane with solvent, and its weight of material ratio is: the crude fish oil ethyl ester: solvent is 1: 0.25～1.2.Decolouring is to use gac, and its weight of material ratio is: the crude fish oil ethyl ester: gac is 1: 0.02～0.08.
The present invention is through repeatedly practising proof, and have following characteristics: method is simple; Starting material (comprising crude fish oil, dehydrated alcohol, solvent etc.) are compared with traditional method, consume significantly to reduce; Quality product improves, and EPA-E+DHA-E content can be up to 76%; Cost reduces greatly; Basically eliminated the pollution of organism to environment.
Below enumerate embodiments of the invention.
Embodiment one
Crude fish oil:
Oleaginousness: 99.02%,
EPA+DHA： (9.66+16.57)％＝26.23％
Acid number: 29.01MG/G.
(1) with the 200KG crude fish oil, the 200KG dehydrated alcohol and the 8.3KG vitriol oil add in the reactor, under nitrogen protection, stir, and heating 75 ℃ of 60 ∽, is reacted after 24 hours, and dehydrated alcohol is reclaimed in distillation.Till about 84 ℃ of still temperature.Raffinate with the 100KG washing is once washed once with the 100KG2% phosphoric acid solution, washes with water to neutrality again, and is static, divides water layer to the greatest extent, gets crude fish oil ethyl ester 207.9KG.Measure:
Content: EPA-E 9.43%
DHA-E 16.01％
EPA-E+DHA-E＝25.44％
Acidity: 0.37ML/G
Peroxide value: 0
(2) with 620KG ethanol, 370KG urea adds in the reactor.Under nitrogen protection, stir, be heated to the urea dissolving after, add above-mentioned crude fish oil ethyl ester 150KG.Continue insulation 20 minutes, be cooled to room temperature then.Elimination urine bag thing.Filtrate is washed with 400KG, tells alcohol-water layer (ethanol to be recycled).(boiling range: 90 ℃ of 60 ∽) dilute, add gac 3.3KG decolouring, the elimination gac distills and reclaims sherwood oil oil reservoir, till having steamed to sherwood oil with the 40KG sherwood oil.Get the refined fish oil that faint yellow height contains EPA-E and DHA-E: 39.5KG.Measure:
Content: EPA-E 26.96%
DHA-E 46.37％
EPA-E+DHA-E＝73.33％
Acidity: 0.03ML/G
Peroxide value: 0.62ML/G
Embodiment two
Crude fish oil:
Oleaginousness: 99%
EPA+DHA＝(9.2％+17.0％)＝26.2％
Acid number: 17.9MG/G
(1) with crude fish oil 200KG, dehydrated alcohol 180KG and vitriol oil 6.2KG add in the reactor, under nitrogen protection, stir, and heating, back flow reaction is after 20 hours.Steam dehydrated alcohol, below handle with embodiment one it (1).Get crude fish oil ethyl ester 201.3KG.Measure:
Content: EPA-E 9.79%
DHA-E 17.11％
EPA-E+DHA-E＝26.90％
Acidity: 0.18ML/G
Peroxide value: 0.3ML/G
(2) 480KG ethanol, 330KG urea add in the reactor, under nitrogen protection, stir; after being heated to the urea dissolving, add above-mentioned crude fish oil ethyl ester 150KG, continue insulation 30 minutes; below operate, but the solvent sherwood oil is used the 70KG hexane instead, gac 5.8KG with embodiment one they (2).Get the refined fish oil that faint yellow height contains EPA-E and DHA-E: 37.1KG.Measure:
Content: EPA-E 27.26%
DHA-E 48.80％
EPA-E+DHA-E＝76.06％
Acidity: 0.03ML/G
Peroxide value: 0.58ML/G.
Embodiment three
Crude fish oil:
Oleaginousness: 99.1%
EPA+DHA＝11.61％+15.63％＝27.24％
Acid number: 41.05MG/G
(1) 200KG crude fish oil, the 340KG dehydrated alcohol, the 18.4KG vitriol oil adds in the reactor, under nitrogen protection, stirs, and heating 50 ℃ of 48 ∽, was reacted 26 hours.Decompression steams dehydrated alcohol, and the still temperature is no more than 55 ℃.Below operation is with embodiment one it (1).Get crude fish oil ethyl ester 203.5KG.Measure:
Content: EPA-E 11.10%
DHA-E 16.72％
EPA-E+DHA-E＝27.82％
Acidity: 0.41ML/G
Peroxide value: 0.96ML/G
(2) 540KG ethanol, 330KG urea add in the reactor, under nitrogen protection, stir, and are heated to the urea dissolving, add above-mentioned crude fish oil ethyl ester 150KG, continue insulation 15 minutes.Be cooled to room temperature, filtering urine bag thing, below operation is with embodiment one they (2).Solvent 180KG hexane, gac 12.2KG.Get the refined fish oil that faint yellow height contains EPA-E+DHA-E: 36.2KG.Measure:
Content: EPA-E 26.89%
DHA-E 48.50％
EPA-E+DHA-E＝75.39％
Acidity: 0.09ML/G
Peroxide value: 0.55ML/G.
Embodiment four
Crude fish oil:
Oleaginousness: 89.8%
EPA+DHA＝(10.8+17.4)％＝28.2％
Acid number: 37.5MG/G
(1) with crude fish oil 200KG, dehydrated alcohol 220KG adds in the reactor, stirs, and 35 ℃ of 30 ∽, feeds hydrogen chloride gas 4.6KG.Keep 35 ℃ of temperature of reaction 30 ∽, and continue logical hydrogenchloride, speed is 0.52KG per hour, react after 6 hours, and left alone without help logical hydrogenchloride, synthermal, continuation was reacted 2 hours, steamed excessive dehydrated alcohol.Raffinate is washed with 200KG, washes once with the 100KG5% phosphoric acid solution again, washes with water to neutrality at last.Static, divide water layer to the greatest extent, get crude fish oil ethyl ester 199.2KG.Measure:
Content:
EPA-E 10.4％
DHA-E 18.22％
EPA-E+DHA-E＝28.62％
Acidity: 0.45ML/G
Peroxide value: 0.81ML/G
(2) with 600KG ethanol, 340KG urea adds in the reactor.Under nitrogen protection, stir, be heated to the urea dissolving after, add above-mentioned crude fish oil ethyl ester 150KG.Continue insulation 30 minutes, be cooled to room temperature then.Leach urine bag thing.Filtrate is washed with 300KG, tells alcohol-water layer, and oil reservoir is with 50KG sherwood oil (120 ℃ of 90 ∽) dilution, add the 6KG activated carbon decolorizing after, the elimination gac, sherwood oil is reclaimed in distillation, till having steamed to sherwood oil.Get the refined fish oil that faint yellow height contains EPA-E+DHA-E: 35.7KG.Measure:
Content: EPA-E 25.71%
DHA-E 47.15％
EPA-E+DHA-E＝72.86％
Acidity: 0.10ML/G
Peroxide value: 0.41ML/G
Embodiment five
Crude fish oil:
Oleaginousness: 99.12%
EPA+DHA＝9.82％+17.88％＝27.70％
Acid number: 31.34MG/G (1) 200KG crude fish oil, the 220KG dehydrated alcohol, 14.8KG phosphoric acid adds in the reactor.Under nitrogen protection, stir, heat, after 26 hours, dehydrated alcohol is reclaimed in distillation in 85 ℃ of reactions of 75 ∽, and raffinate with the 150KG washing is once washed once with the 100KG1% phosphoric acid solution again, washes with water at last to neutrality, gets crude fish oil ethyl ester 198.6KG.Measure:
Content: EPA-E 9.44%
DHA-E 17.03％
EPA-E+DHA-E＝26.47％
Acidity: 0.22ML/G
Peroxide value: 0.48ML/G
(2) 540KG ethanol, 350KG urea add in the reactor, under nitrogen protection; stir, be heated to the urea dissolving, add above-mentioned crude fish oil ethyl ester 150KG; continue insulation after 30 minutes, be chilled to room temperature, filtering urine bag thing; filtrate water 150KG washes; divide and go alcohol-water solution, add 90KG sherwood oil (boiling range: 90 ℃ of 60 ∽) dilute, behind the adding 9.5KG activated carbon decolorizing in the oil reservoir; the elimination gac, sherwood oil is reclaimed in distillation.Get the refined fish oil that faint yellow height contains EPA-E+DHA-E: 33.4KG.Measure:
Content: EPA-E 27.04%
DHA-E 45.23％
EPA-E+DHA-E＝72.27％
Acidity: 0.25ML/G
Peroxide value: 0.40ML/G.
Claims (5)
1. method that contains the ethyl polyenoate refined fish oil from crude fish oil production; it is characterized in that; with crude fish oil in the presence of an acidic catalyst; with excessive dehydrated alcohol; at 30～85 ℃; under the nitrogen protection; carry out transesterification reaction; the weight of material ratio of reaction is: crude fish oil: dehydrated alcohol: acid is 1: 0.9～1.8: 0.03～0.10; reaction finishes; after boiling off dehydrated alcohol; raffinate washes with water once; wash once with the phosphoric acid dilute solution again; wash with water at last to neutrality, branch vibration layer gets the crude fish oil ethyl ester; ethanol and urea are added in the reactor; under nitrogen protection, stir, be heated to the urea dissolving after; add above-mentioned crude fish oil ethyl ester; crude fish oil ethyl ester: ethanol: the weight of material ratio of urea is 1: 3～4.5: 2.1～2.5, continues insulation after 10～30 minutes, is chilled to room temperature; elimination urine bag thing; after the filtrate washing, divide and remove alcohol-water layer, oil reservoir solvent cut; add activated carbon decolorizing; the filtering gac boils off solvent, gets the faint yellow refined fish oil that contains EPA-EE and docosahexenoic acid ethyl ester.
2. method according to claim 1 is characterized in that, an acidic catalyst is the vitriol oil, hydrogenchloride or phosphoric acid.
3. method according to claim 1 is characterized in that, the phosphoric acid dilute solution is 1～5% phosphate aqueous solution.
4. method according to claim 1 is characterized in that, the dilution solvent of activated carbon decolorizing is sherwood oil or hexane, and its weight of material ratio is: the crude fish oil ethyl ester: solvent is 1: 0.25～1.2.
5. method according to claim 1 is characterized in that, uses activated carbon decolorizing, and its weight of material ratio is: the crude fish oil ethyl ester: gac is 1: 0.02～0.08.
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| Application Number | Priority Date | Filing Date | Title |
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| CN99114410A CN1084380C (en) | 1999-08-30 | 1999-08-30 | Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil |
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| CN99114410A CN1084380C (en) | 1999-08-30 | 1999-08-30 | Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil |
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| CN1263145A CN1263145A (en) | 2000-08-16 |
| CN1084380C true CN1084380C (en) | 2002-05-08 |
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| CN99114410A Expired - Fee Related CN1084380C (en) | 1999-08-30 | 1999-08-30 | Process for producing refined fish oil with high polyenoic acid ethyl ester content from crude fish oil |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20032247A1 (en) * | 2003-11-19 | 2005-05-20 | Tiberio Bruzzese | INTERACTION OF POLAR DERIVATIVES OF COMPOUNDS INSATURATED WITH INORGANIC SUBSTRATES |
| CN103509651B (en) * | 2012-06-27 | 2015-01-07 | 浙江海洋学院 | A method for extracting and enriching ethyl ester type fish oil from fish oil refining by-products |
| CN103396310B (en) * | 2013-07-25 | 2015-02-25 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
| CN104611128B (en) * | 2015-01-13 | 2017-09-22 | 浙江工业大学 | Fishy smell-removed fish oil and preparation method thereof |
| CN106349070A (en) * | 2016-08-31 | 2017-01-25 | 山东康曼生物科技有限公司 | Technology for producing Omega-3-ethyl gallate 90 from low-content ethyl ester fish oil |
| CN115109654A (en) * | 2021-03-23 | 2022-09-27 | 福建海富特生物科技股份有限公司 | Ethyl esterification production process of edible fish oil |
| CN113717789A (en) * | 2021-09-18 | 2021-11-30 | 广州市珺琳轩生物科技有限公司 | Antioxidant refining and purifying method of fish oil |
| CN114057574A (en) * | 2021-12-03 | 2022-02-18 | 浙江工商大学 | Method for preparing high-purity EPA ethyl ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132195A (en) * | 1995-11-24 | 1996-10-02 | 清华大学 | Technique for prodn. of fish oil polyene fatty acid ethylester |
| US5679809A (en) * | 1994-05-09 | 1997-10-21 | Nestec S.A. | Concentrate of polyunsaturated fatty acid ethyl esters and preparation thereof |
| CN1222564A (en) * | 1998-01-05 | 1999-07-14 | 山东禹王制药有限公司 | Industrial production of highly unsaturated fatty acid |
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1999
- 1999-08-30 CN CN99114410A patent/CN1084380C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679809A (en) * | 1994-05-09 | 1997-10-21 | Nestec S.A. | Concentrate of polyunsaturated fatty acid ethyl esters and preparation thereof |
| CN1132195A (en) * | 1995-11-24 | 1996-10-02 | 清华大学 | Technique for prodn. of fish oil polyene fatty acid ethylester |
| CN1222564A (en) * | 1998-01-05 | 1999-07-14 | 山东禹王制药有限公司 | Industrial production of highly unsaturated fatty acid |
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