CN107216946A - The minimizing technology of plasticiser in a kind of fish oil - Google Patents
The minimizing technology of plasticiser in a kind of fish oil Download PDFInfo
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- CN107216946A CN107216946A CN201610165422.3A CN201610165422A CN107216946A CN 107216946 A CN107216946 A CN 107216946A CN 201610165422 A CN201610165422 A CN 201610165422A CN 107216946 A CN107216946 A CN 107216946A
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- Prior art keywords
- fish oil
- organic solvent
- eluent
- plasticiser
- silica gel
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 59
- 235000021323 fish oil Nutrition 0.000 title claims abstract description 55
- 238000005516 engineering process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003480 eluent Substances 0.000 claims abstract description 32
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 20
- 239000012488 sample solution Substances 0.000 claims abstract description 17
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 15
- 238000010828 elution Methods 0.000 claims abstract description 13
- 238000004332 deodorization Methods 0.000 claims abstract description 8
- 239000000523 sample Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 238000007670 refining Methods 0.000 claims abstract description 3
- 235000019198 oils Nutrition 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000741 silica gel Substances 0.000 claims description 17
- 229910002027 silica gel Inorganic materials 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- -1 2 Number eluant Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 241000251468 Actinopterygii Species 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 5
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 abstract description 5
- 125000005456 glyceride group Chemical group 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 28
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 13
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 13
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 13
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 13
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 12
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000008157 edible vegetable oil Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 239000004519 grease Substances 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000009874 alkali refining Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000001525 mentha piperita l. herb oil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000019477 peppermint oil Nutrition 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 208000026106 cerebrovascular disease Diseases 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- JYGYEBCBALMPDC-UHFFFAOYSA-N heptane;propan-2-one Chemical compound CC(C)=O.CCCCCCC JYGYEBCBALMPDC-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000008397 Ganoderma lucidum Species 0.000 description 1
- 235000001637 Ganoderma lucidum Nutrition 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 206010067572 Oestrogenic effect Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 206010008118 cerebral infarction Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GLCGEJFIZRSXBL-UHFFFAOYSA-N dodeca-1,3,5,7,9,11-hexaene Chemical compound C=CC=CC=CC=CC=CC=C GLCGEJFIZRSXBL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 231100000417 nephrotoxicity Toxicity 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229940124549 vasodilator Drugs 0.000 description 1
- 239000003071 vasodilator agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C11B3/10—Refining fats or fatty oils by adsorption
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
- A23D9/04—Working-up
Abstract
The invention discloses the method that plasticiser in a kind of fish oil is removed, 1) fish oil after refining is dissolved in low polar organic solvent under conditions of 20~50 DEG C, to obtain sample solution；2) silica gel column chromatography first loaded is balanced with the low polar organic solvent, 1) the middle sample solution dissolved is pumped into silica gel column chromatography；3) after after end of the sample, using gradient elution, successively with No. 1, No. 2, No. 3 eluents, preceding part is with No. 1 eluent, and positive part is with No. 2 eluents, and rear part is with No. 3 eluents, finally balanced again with No. 1 eluant, eluent, the chromatographic column after balance may be reused；4) after eluent Fractional Collections, preceding part and rear part are discarded, positive part eluent is collected, the recycling design that is concentrated under reduced pressure obtains plasticiser after deodorization and detects qualified food-grade fish oil again.The content that effectively removes polyunsaturated fatty acid glyceride in most of impurity, fish oil by the inventive method can improve 3~5%.
Description
Technical field
It is more particularly to a kind of to remove fish the present invention relates to a kind of method for removing the impurity in fish oil
The method of plasticiser in oil, belongs to fats and oils processing and technical field of food safety.
Background technology
Fish oil is a kind of natural health product extracted out of marine fishes body, and fish oil is rich in
ω -3 types polyunsaturated fatty acid (PUFA), particularly eicosapentaenoic acid (EPA) and two
Dodecahexaene acid (DHA), is to health and intelligence with abundant nutritive value
Power, which is developed, the physiological activator of significant impact, with regulation blood fat, suppress platelet aggregation,
Prevention of arterial atherosis, prevention cardiovascular and cerebrovascular disease, reduction blood viscosity, prevention brain blood
All multiactions such as bolt and cerebral infarction, antithrombotic, vasodilator and improvement eyesight.Therefore, it is rich in
EPA and DHA fish oil has highly important nutrition and medical value.
Plasticiser is also known as plasticizer, and they are the systems of about 30 kinds of esters of phthalic acid formation
Claim, current phthalate plasticiser (PAEs) is the main body of plasticiser, its yield
Plasticiser total output 80% is accounted for, plastic shaping is industrially widely used in, particularly for polychlorostyrene
Copolymer from ethylene and vinyl chloride, is also used for the products such as rubber, cellulose, dyestuff, dispersant.
Due to production, using and processing procedure in release, therefore it can pass through number of ways
Contaminated food, such as water, soil, air, packaging material for food.Phthalate thing
Matter at normal temperatures be water white transparency oily liquids, be insoluble in water, be soluble in methanol, ethanol,
A variety of organic solvents such as ether, belong to liposoluble substance, are easily detected in oily food.
Phthalate has estrogenic effect, hepatotoxicity wind agitation, renal toxicity, endangers men and women
Reproductive system, triggers infant's hormonal imbalance, causes sex premature, in some instances it may even be possible to carcinogenic.Due to
To the potential hazard of the mankind, European Union, the U.S., Japan, China are successively to phthalate
Material is included in priority pollutants.DEHP (O-phthalics in phthalate plasticiser
Sour two (2- ethyls) own esters), DBP (dibutyl phthalate) be major pollutants, grain
Middle DEHP recall rates highest.China, which defends, does (2011) No. 551 file regulations of supervision letter, food,
DEHP (phthalic acid two (2- ethylhexyls), DINP (phthalic acids in food additives
Dinonyl), DBP (dibutyl phthalate) maximum allowable residual quantity be respectively
1.5mg/kg, 9.0mg/kg and 0.3mg/kg.
It is extra large in the last few years due to being influenceed by environmental factors such as surface soil, water source and air
Pollute in the continuous cumulative function of food chain between gradually serious and marine organisms, hair fish oil in ocean
Inevitably contain all kinds of environmental contaminants.These environmental contaminants for example residues of pesticides, heavy metal,
Bioxin, BaP and plasticiser etc. constantly invade ocean, cause the marine eco-environment continuous
Deteriorate, this kind of material is permanently present in fish oil and serious toxicity consequence caused by human body has been drawn
Play the highest attention in the field.In consideration of it, as there is serious danger known to a class to health
Harmful material, can remove this to greatest extent with a kind of convenient, the economic technique of industrial production
Pollutant, minimum is reduced to by the content of plasticiser in fish oil, or even makes to examine in fish oil
Measure this pollutant, it is clear that be very important.
On removing the environment such as removing heavy metals, agricultural chemicals, bioxin and BaP in current oil prodution industry
The research of pollutant and report are more, and the technique study report removed to plasticiser is then less.
As open source literature " attributional analysis of food-grade deep sea fish oil and control " [Chinese oil,
2012,37 (5)：44-47] in describe heavy metal, agriculture in fish oil refinery practice in detail
The research of the method for analysis, control and the removal of medicine, bioxin and BaP and report, still
The research on plasticiser control and pollution is not reported.Open source literature " plasticiser in edible oil
Pollution channel and analysis method progress " [Chinese oil, 2013,38 (5)：1-5]
In describe in the plasticiser contamination phenomenon and edible oil of generally existing in current edible oil and plastify
The ways and means of agent detection, but do not report the research method that plasticiser is removed in edible oil
And means.Open source literature " safety of plasticiser and grain and oil product " [Chinese oil, 2013,
38(4)：1-4] in describe plasticiser harm, grain and oil processing in plasticiser source and
The method and approach of pollution are controlled, the grease that plasticiser has not been polluted equally yet removes modeling
The method and means of agent.
Chinese patent CN103710153A discloses adjacent benzene two in a kind of quick removal peppermint oil
The method of formate ester plasticiser, changes method by peppermint oil, alkali and water Hybrid Heating, utilizes alkali
Phthalate plasticiser is hydrolyzed, then divides liquid to remove water layer, reaches in oil removing and plastifies
The purpose of agent., will not water in alkaline aqueous solution but the main component of peppermint oil is menthol
Solution, and the main component of fish oil is triglycerides, is added after alkaline aqueous solution in hydrolysis plasticiser
While also can hydrolyzing triglyceride, can more seriously emulsify causes to be layered, thus should
Method is not suitable for the removal of plasticiser in fish oil.
The B of Chinese patent CN 102965192 disclose a kind of remove in ganoderma lucidum spore oil raw material and moulded
The method that agent is remained and polluted, this method is using hyperlink carbon dioxide in different pressures and temperature
Plasticiser in the change in polarity of degree, selective extraction grease, but the process equipment requires high,
Investment is big, and cost is high, without industrial value.
Chinese patent CN104705419A discloses a kind of side for removing plasticiser in edible oil
Method, this method carries out multiple liquid-liquid extraction, extraction to edible oil using a large amount of methanol as solvent
Methanol and edible oil are separated after taking, last recycling methanol.Due to phthalate modeling
Agent is fat-soluble compound in itself, and the solubility in vegetable oil is more than dissolving in methyl alcohol
Degree, so it is low, it is necessary to a large amount of molten to remove plasticiser efficiency using the raw material of above-mentioned liquid-liquid extraction
Agent is extracted repeatedly, and solvent consumption is big, wastes time and energy, and can greatly increase being produced into for fish oil
This.
Chinese patent CN102295989A discloses phthalic acid ester in removal vegetable and animals oils
The molten of phthalate material can be dissolved and be adsorbed to the method for class plasticiser, this method utilization
Agent utilizes work(of the back washing agent to dissolving and the absorption of phthalate material as back washing agent
Can, realize the purpose for removing phthalate plasticiser in animal and plant fat.Equally, by
Fat-soluble in phthalate plasticiser determines that its solubility in oil is big, needs
Substantial amounts of organic solvent is extracted repeatedly to be removed, and efficiency is low, and technique is cumbersome, remove cost high.
In view of to there is technical process on plasticiser in grease is removed cumbersome for above-mentioned prior art, it is raw
Produce cost height, industrial applications and be worth low defect, fish can be removed to greatest extent by finding one kind
Plasticiser in oil, and technical process is easy, production cost is low, be adapted to large-scale industrial production
Fish oil technique be very important.
The content of the invention
The method that the present invention removes plasticiser in food-grade fish oil for a kind of silica gel column chromatography of offer.
The separation principle of silica gel column chromatography is different and obtain according to absorption affinity of the material on silica gel
To separation, the larger material of polarity is easily by silica gel absorption, and the weaker material of polarity is difficult by silica gel
Absorption, whole chromatography process is Adsorption and desorption, adsorb again, desorption process again.Adjacent benzene two
Formate ester plasticiser due to be macromolecular Ester, its polarity is weaker, phthalic acid
The polarity of esters is less than the polarity of the triglycerides in grease, it is considered to utilize phthalate
Plasticiser and polyunsaturated fatty acid triglycercide polarity difference in fish oil, utilize opposed polarity
Organic solvent gradient elution, to reach the purpose of removing plasticiser.
The technical problem to be solved in the present invention is to provide for a kind of removal of plasticiser in fish oil
Method, the minimizing technology comprises the following steps：Step 1)：Fish oil after refining is existed
It is dissolved under conditions of 20~50 DEG C in low polar organic solvent, to obtain sample solution；Wherein, institute
State the one kind of low polar organic solvent in n-hexane, hexamethylene, petroleum ether and normal heptane；
Step 2)：The silica gel column chromatography first loaded is balanced with the low polar organic solvent, so
Afterwards by step 1) in the sample solution that has dissolved be pumped into the speed of 0.1~1 times of column volume/hour
In silica gel column chromatography；Step 3)：After after end of the sample, using gradient elution, successively with 1
Number eluant, eluent, No. 2 eluant, eluents, No. 3 eluents, (preceding part refers to that rudimentary polarity is miscellaneous to preceding part
Matter component, is eluted out at first) with No. 1 eluent, (positive part refers to medium pole to positive part
Property impurity composition, i.e., required for component, median elution comes out) with No. 2 eluents,
Part (rear part refers to highly polar impurity composition, is finally eluted out) is with No. 3 eluents afterwards,
Finally balanced again with No. 1 eluant, eluent, the chromatographic column after balance may be reused；And step
4)：After eluent Fractional Collections, preceding part and rear part are discarded, positive part eluent, decompression is collected
Concentration and recovery solvent obtains plasticiser after deodorization and detects qualified food-grade fish oil again.
In the preferred technical solution of the present invention, it is preferable that the chromatographic stationary phases are nonbonding silicon
Glue, particle diameter is 60~400 mesh indefinite form silica gel.It is highly preferred that the particle diameter is 100~200
Mesh indefinite form silica gel.
In the preferred technical solution of the present invention, it is preferable that the quality of fish oil is in the sample solution
0.05~0.5 times of silica gel chromatographic column filling material.It is highly preferred that the quality of fish oil is in the sample solution
0.1~0.2 times of silica gel chromatographic column filling material.
In the preferred technical solution of the present invention, it is preferable that No. 1 eluant, eluent is that low polarity has
Machine solvent；No. 2 eluant, eluents and No. 3 eluant, eluents be respectively low polar organic solvent with
The mixed solvent of highly polar organic solvent；Wherein, low polarity is organic molten in No. 2 eluant, eluents
Percent by volume >=60% that agent is accounted for, >=70%, >=80% or >=90%, No. 3 elutions
Highly polar organic solvent percentage >=60% in agent, >=70%, >=80% or >=90%.
In the preferred technical solution of the present invention, it is preferable that the low polar organic solvent is selected from just
One kind in hexane, hexamethylene, normal heptane, petroleum ether.It is highly preferred that the low polarity has
Machine solvent is normal heptane.
In the preferred technical solution of the present invention, it is preferable that the highly polar organic solvent is selected from second
One kind in acetoacetic ester, isopropanol, acetone and methyl tertiary butyl ether(MTBE).It is highly preferred that the height
Polar organic solvent is acetone.
According to the minimizing technology of the present invention, alkali refining fish oil can be alkali refining oil, bleached oil, deodorization
Oil or winterized oil, preferably bleached oil.Bleached oil is removed after plasticiser by above-mentioned silica gel column chromatography,
Obtain meeting the product oil of plasticiser quality standard after deodorization again.The alkali refining oil refers to hair
Oil of the fish oil after degumming and depickling processing；The bleached oil refer to mao fish oil by degumming,
Oil after depickling and decolorization；The deodorised oil refers to that mao fish oil passes through degumming, depickling, taken off
Oil after color and deodorization processing.The winterized oil refer to mao fish oil by degumming, depickling, decolouring,
Oil after deodorization and winterization processing；
A kind of Advantageous effect for removing the method for plasticiser in edible oil provided by the present invention
It is really：1) removal efficiency is high, and the inventive method removes plasticiser effect in fish oil significantly, can
The exceeded fish oil of all kinds of plasticisers is effectively handled, is detected through third party testing agency, after processing
Fish oil meets the standard requirement of national plasticiser, effectively removes most of low polarity and height
The content of polyunsaturated fatty acid glyceride can improve 3~5% in the impurity of polarity, fish oil,.2)
With strong points, the inventive method targetedly removes the plasticiser in grease, in grease
Other compositions are substantially without influence, mild condition, the grease outward appearance after processing, color, physics and chemistry
Matter is significantly lifted.3) processing speed is fast, cost is low, the inventive method disposal ability
Greatly, method is simple, quick and with low cost, and silica gel column chromatography and organic solvent can be followed
Ring is used, it is easy to the large-scale production of industrialization.
Brief description of the drawings
Fig. 1 represents the process chart of the present invention.
Embodiment
Below with reference to drawings and examples, the present invention will be further described, implementation of the invention
Example is merely to illustrate technical scheme, and the non-limiting present invention.
Embodiment 1
Chromatographic column 60 × 800mm, the interior mesh silica gel 500g of filling 100~200, column volume is
800mL, i.e. 1BV=800ml, are first balanced using preceding with 2BV normal heptane.
Take 100g decolourize after fish oil (EPA and DHA content are 29.5% or so in the fish oil,
Plasticiser detection DBP is 1.5mg/kg, and DEHP is 24mg/kg, other not detect), plus
Enter 100ml normal heptane in after 20~30 DEG C of stirring and dissolvings to obtain sample solution, will by preparing pump
The sample solution is pumped into silica gel column chromatography with the speed of 0.1~1 times of column volume/hour, loading knot
Shu Hou, then uses 2BV normal heptane, 2BV 10% acetone-normal heptane, 2BV70% successively
Acetone-normal heptane gradient elution.The preceding part of Fractional Collections, positive part and rear part, wherein positive part is 76.3g,
EPA and DHA content are that 32.6%, DEHP is 0.2mg/kg, other not detect；Moulded
Agent detects qualified food-grade fish oil.
Embodiment 2
Chromatographic column 60 × 800mm, interior filling 60-100 mesh silica gel 500g, column volume is
800mL, i.e. 1BV=800ml, are first balanced using preceding with 2BV n-hexane.
Taking the fish oil after 75g decolourings, (EPA and DHA content are 29.5% or so in the fish oil, modeling
Agent detection DBP is 1.5mg/kg, and DEHP is 24mg/kg, other not detect), add
75ml n-hexanes in after 30~40 DEG C of stirring and dissolvings to obtain sample solution, will be described by preparing pump
Sample solution is pumped into silica gel column chromatography with the speed of 0.1~1 times of column volume/hour, after end of the sample,
Then 3BV n-hexane, 1.5BV 15% ethyl acetate-hexane, 2BV60% is used successively
Ethyl acetate-hexane gradient elution.The preceding part of Fractional Collections, positive part and rear part, wherein positive part
For 72.3g, EPA and DHA content are 32.9%, and plasticiser is not detected；Obtain plasticiser inspection
Survey qualified food-grade fish oil.
Embodiment 3
Chromatographic column 60 × 800mm, the interior mesh silica gel 500g of filling 200~300, column volume is
800mL, i.e. 1BV=800ml, are first balanced using preceding with 2BV hexamethylene.
Taking the fish oil after 25g deodorizations, (EPA and DHA content are 28.5%, plasticiser in the fish oil
Detection DBP is 1.1mg/kg, and DEHP is 7.9mg/kg, other not detect), add 75ml
Hexamethylene in after 40~50 DEG C of stirring and dissolvings to obtain sample solution, by preparing pump by the loading
Liquid is pumped into silica gel column chromatography with the speed of 0.1~1 times of column volume/hour, after end of the sample, so
Afterwards successively with 2BV hexamethylene, 1.5BV 15% isopropanol-hexamethylene, 2BV60% isopropyls
Alcohol-hexamethylene gradient elution.The preceding part of Fractional Collections, positive part and rear part, wherein positive part is 21.5g,
EPA and DHA content are 31.9%, and plasticiser is not detected；Obtain plasticiser detection qualified
Food-grade fish oil.
Embodiment 4
Chromatographic column 60 × 800mm, the interior mesh silica gel 250g of filling 300~400, column volume is
400mL, i.e. 1BV=400ml, are first balanced using preceding with 2BV petroleum ether.
Taking the fish oil after 125g winterization, (EPA and DHA content are 31.4% in the fish oil, plasticizing
Agent detection DBP is 0.8mg/kg, and DEHP is 5.8mg/kg, other not detect), add 125ml
Normal heptane in after 20~30 DEG C of stirring and dissolvings to obtain sample solution, by preparing pump by the loading
Liquid is pumped into silica gel column chromatography with the speed of 0.1~1 times of column volume/hour, after end of the sample, so
Use 2BV petroleum ether, 2BV 10% acetone-petroleum ether, 2BV80% acetone-petroleums successively afterwards
Ether gradient elution.The preceding part of Fractional Collections, positive part and rear part, wherein positive part is 105.4g, EPA
It is 32.9% with DHA content, plasticiser is not detected；Obtain plasticiser and detect qualified food
Level fish oil.
Embodiment 5
Chromatographic column 60 × 800mm, the interior mesh silica gel 250g of filling 100~200, column volume is
400mL, i.e. 1BV=400ml, are first balanced using preceding with 2BV normal heptane.
Taking the fish oil after 75g winterization, (EPA and DHA content are 31.4%, plasticiser in the fish oil
Detection DBP is 0.8mg/kg, and DEHP is 5.8mg/kg, other not detect), add 755ml
Normal heptane in after 25~30 DEG C of stirring and dissolvings to obtain sample solution, by preparing pump by the loading
Liquid is pumped into silica gel column chromatography with the speed of 0.1~1 times of column volume/hour, after end of the sample, so
Use 2BV normal heptane, 1BV 20% methyl tertiary butyl ether(MTBE)-normal heptane, 1BV90% successively afterwards
Methyl tertiary butyl ether(MTBE)-normal heptane gradient elution.The preceding part of Fractional Collections, positive part and rear part, wherein
Positive part is 55.6g, and EPA and DHA content are 34.9%, and plasticiser is not detected；Plastified
Agent detects qualified food-grade fish oil.
The technical scheme in the embodiment of invention is checked, is fully described by above, described
Embodiment be only the present invention a part of embodiment, rather than whole embodiment.It is based on
Embodiment in the present invention, those of ordinary skill in the art institute under the premise of creativeness is not made
The all other embodiment obtained.
Claims (10)
1. a kind of minimizing technology of plasticiser in fish oil, the minimizing technology comprises the following steps：
Step 1)：Fish oil after refining is dissolved in low polarity under conditions of 20~50 DEG C organic molten
In agent, to obtain sample solution；Wherein, the low polar organic solvent is selected from n-hexane, hexamethylene
One kind in alkane, petroleum ether and normal heptane；
Step 2)：The silica gel column chromatography first loaded is balanced with the low polar organic solvent,
Then by step 1) in the sample solution that has dissolved with the speed pump of 0.1~1 times of column volume/hour
Enter in silica gel column chromatography；
Step 3)：After after end of the sample, using gradient elution, successively with No. 1 eluant, eluent, 2
Number eluant, eluent, No. 3 eluents, preceding part is with No. 1 eluent, and positive part is with No. 2 elutions
Agent is eluted, and rear part finally balances the height in chromatogram with No. 1 eluant, eluent again with No. 3 eluents
Chromatographic column after polar organic solvent, balance may be reused；And
Step 4)：After eluent Fractional Collections, preceding part and rear part are discarded, positive part elution is collected
Liquid, the recycling design that is concentrated under reduced pressure obtains plasticiser after deodorization and detects qualified food-grade fish again
Oil.
2. according to the method described in claim 1, wherein, the chromatographic stationary phases be nonbonding
Silica gel, particle diameter is 60~400 mesh indefinite form silica gel.
3. method according to claim 2, wherein, the particle diameter be 100~200 mesh not
Sizing silica gel.
4. according to the method described in claim 1, wherein, the matter of fish oil in the sample solution
Measure as 0.05~0.5 times of silica gel chromatographic column filling material.
5. according to the method described in claim 1, wherein, the matter of fish oil in the sample solution
Measure as 0.1~0.2 times of silica gel chromatographic column filling material.
6. according to the method described in claim 1, wherein, No. 1 eluant, eluent be low pole
Property organic solvent；No. 2 eluant, eluents and No. 3 eluant, eluents are respectively that low polarity is organic molten
Agent and the mixed solvent of highly polar organic solvent；Wherein, in No. 2 eluant, eluents there be low polarity
Percent by volume >=60% that machine solvent is accounted for, >=70%, >=80% or >=90%, described No. 3
Highly polar organic solvent percentage >=60% in eluant, eluent, >=70%, >=80% or >=90%.
7. method according to claim 6, wherein, the low polar organic solvent choosing
One kind from n-hexane, hexamethylene, normal heptane, petroleum ether.
8. method according to claim 7, wherein, the low polar organic solvent is
Normal heptane.
9. method according to claim 6, wherein, the highly polar organic solvent choosing
One kind from ethyl acetate, isopropanol, acetone and methyl tertiary butyl ether(MTBE).
10. method according to claim 9, wherein, the highly polar organic solvent is
Acetone.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112694947A (en) * | 2020-12-01 | 2021-04-23 | 晨光生物科技集团股份有限公司 | Method for removing plasticizer from pepper essential oil and pepper essential oil |
| CN113122377A (en) * | 2019-12-30 | 2021-07-16 | 丰益(上海)生物技术研发中心有限公司 | Method for removing plasticizer in oil refining process |
| CN113201397A (en) * | 2021-04-08 | 2021-08-03 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113122377A (en) * | 2019-12-30 | 2021-07-16 | 丰益(上海)生物技术研发中心有限公司 | Method for removing plasticizer in oil refining process |
| CN112694947A (en) * | 2020-12-01 | 2021-04-23 | 晨光生物科技集团股份有限公司 | Method for removing plasticizer from pepper essential oil and pepper essential oil |
| CN113201397A (en) * | 2021-04-08 | 2021-08-03 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
| CN113201397B (en) * | 2021-04-08 | 2024-02-23 | 四川国为制药有限公司 | Method for reducing plasticizer content in fish oil product |
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