CN114214116B - Antarctic krill extract dearsenization treatment method and application of adsorbent in dearsenization - Google Patents
Antarctic krill extract dearsenization treatment method and application of adsorbent in dearsenization Download PDFInfo
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- 241000239366 Euphausiacea Species 0.000 title claims abstract description 142
- 239000003463 adsorbent Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000000284 extract Substances 0.000 title claims abstract description 40
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 112
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229940106134 krill oil Drugs 0.000 claims abstract description 100
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 57
- 241000239370 Euphausia superba Species 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010992 reflux Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- 235000013372 meat Nutrition 0.000 claims description 31
- 102000004169 proteins and genes Human genes 0.000 claims description 30
- 108090000623 proteins and genes Proteins 0.000 claims description 30
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 17
- 229940088598 enzyme Drugs 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 14
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- 238000001291 vacuum drying Methods 0.000 claims description 13
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- 229940055729 papain Drugs 0.000 claims description 7
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- 239000012535 impurity Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 108090000145 Bacillolysin Proteins 0.000 claims description 3
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- 102000035092 Neutral proteases Human genes 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
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- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000007065 protein hydrolysis Effects 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 description 16
- 238000005070 sampling Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 2
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000005118 dietary health Nutrition 0.000 description 2
- OGGXGZAMXPVRFZ-UHFFFAOYSA-N dimethylarsinic acid Chemical compound C[As](C)(O)=O OGGXGZAMXPVRFZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- -1 EDTA complexes metallic arsenic ions Chemical class 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229950004243 cacodylic acid Drugs 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
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- 239000002775 capsule Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DVUATXGAAOINPS-UHFFFAOYSA-N dimethoxyarsinic acid Chemical compound CO[As](O)(=O)OC DVUATXGAAOINPS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
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- 231100000211 teratogenicity Toxicity 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J3/00—Working-up of proteins for foodstuffs
- A23J3/30—Working-up of proteins for foodstuffs by hydrolysis
- A23J3/32—Working-up of proteins for foodstuffs by hydrolysis using chemical agents
- A23J3/34—Working-up of proteins for foodstuffs by hydrolysis using chemical agents using enzymes
- A23J3/341—Working-up of proteins for foodstuffs by hydrolysis using chemical agents using enzymes of animal proteins
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/006—Refining fats or fatty oils by extraction
-
- 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
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Peptides Or Proteins (AREA)
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- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Meat, Egg Or Seafood Products (AREA)
Abstract
The invention relates to a method for removing heavy metal arsenic in an antarctic krill extract. The method comprises the following steps: (1) Dispersing the euphausia superba peptide powder in water or an acid solution to obtain a mixed solution I; (2) Mixing the mixed solution I with an adsorbent to perform dearsenification treatment, and removing the adsorbent to obtain a mixed solution II; (3) Performing desolventizing treatment on the mixed solution II to obtain dearsenified antarctic krill peptide powder; or (1) dissolving the antarctic krill oil in an organic solvent to obtain a mixed solution A; (2) And mixing the mixed solution A with an adsorbent, refluxing and stirring, performing rotary evaporation, and filtering to obtain the dearsenified antarctic krill oil. The invention greatly reduces the content of total arsenic in the euphausia superba extract and obviously improves the safety of the euphausia superba extract. The method disclosed by the invention is simple and convenient to operate, the used reagent is easy to obtain, the adsorption effect is excellent, the problem about total arsenic removal in the euphausia superba extract is solved, and the excellent effect of removing arsenic is obtained.
Description
Technical Field
The invention belongs to the technical field of food processing, and relates to an arsenic removal treatment method of an antarctic krill extract, and application of a specific adsorbent in obtaining the antarctic krill extract (mainly comprising antarctic krill peptide and antarctic krill oil) with low arsenic content, wherein the antarctic krill oil also comprises astaxanthin.
Background
The euphausia superba belongs to small crustaceans in euphausiiales of crustaceans, has extremely high nutritional value, and has high protein content and lipid content in the euphausia superba meat, so the euphausia superba is an ideal food for human beings, and is compared with the protein resource warehouse of the human beings in the future. Antarctic krill mainly feeds on plankton and algae and has the characteristic of enriching trace elements or heavy metals through a food chain and other ways, so that the Antarctic krill is a biological resource with great development and utilization potential, and the food safety of related products is concerned. Many researchers found that antarctic krill contains a small amount of arsenic, and the arsenic is transferred to the final product to different degrees in the subsequent processing process, so that the content of arsenic in krill extracts such as krill oil and krill protein peptides is high.
Arsenic in antarctic krill is mostly organic arsenic and a small amount of inorganic arsenic. Inorganic arsenic has high toxicity, teratogenicity and carcinogenesis; although many experts and scholars state that most of the organic arsenic is low-toxic or non-toxic, the long-term intake of the organic arsenic is not beneficial to human body and has a certain potential risk. In the food processing process of antarctic krill, the content of arsenic needs to be reduced as much as possible to prevent arsenic enrichment so as to ensure the safety of food and the dietary health of human beings.
Guo Yingying et al, in the article "analysis of arsenic content in Euphausia superba and products thereof and evaluation of safety", disclose: the total arsenic and inorganic arsenic content in the antarctic krill and the product thereof are respectively detected by adopting hydride generation, atomic fluorescence spectrometry and liquid chromatography-atomic fluorescence spectrometry, and the result shows that: the total arsenic content in the euphausia superba protein peptide powder, the euphausia superba oil and capsule products thereof is relatively high.
Wang Song et al, used an LC-plasma mass spectrometer to analyze the forms of arsenic compounds in antarctic krill and antarctic krill oil, and obtained total arsenic content in the krill was 2mg/kg, and the total arsenic content of the krill oil extracted by an ethanol solution with a volume fraction of 95% reached 8.3mg/kg, wherein the content of AsB was 7.3mg/kg, which accounted for 87.9% of the total arsenic content. Arsenic in antarctic krill is mostly organic arsenic and a small amount of inorganic arsenic which is toxic, teratogenic and carcinogenic; although most of the organic arsenic is nontoxic, the long-term intake of the organic arsenic is not beneficial to human bodies and has certain potential risks. In the food processing process of antarctic krill, the content of arsenic needs to be reduced as much as possible to prevent arsenic enrichment so as to ensure the safety of food and the dietary health of human beings.
As for the removal method of arsenic, at present, there are more common methods: the precipitation method, the adsorption method, the membrane technology and the biological method are mainly used for removing inorganic arsenic in industry, and the following documents are disclosed for removing heavy metals in related products of antarctic krill:
at present, organic arsenic removal in foods, particularly in antarctic krill extracts, is not reported, and at present, the industry of the antarctic krill extracts has no policy for exceeding arsenic, so that the content of arsenic in the antarctic krill extracts is reduced to 1mg/kg of food standard, which is a technical problem to be solved urgently.
CN110724596A discloses a method for removing arsenic from antarctic krill oil, which provides a method for removing arsenic from antarctic krill oil, wherein the antarctic krill oil is dispersed in an organic solvent, EDTA is added to graft magnetic chitosan, and after ultrasonic oscillation reaction, the EDTA-grafted magnetic chitosan is removed to obtain the antarctic krill oil from which the arsenic is removed.
However, EDTA complexes metallic arsenic ions and is very ineffective for organic arsenic removal.
Patent CN112126517a provides a method for removing arsenic from antarctic krill oil by using iron-loaded silica gel and iron-loaded multifunctional silica gel material, which can remove arsenic to below 1mg/kg, but the organic arsenic in antarctic krill is mainly organic arsenic such as arsenic betaine, arsenic sugar, arsenic choline and the like. The invention focuses on methyl arsenic acid, dimethyl arsenic acid and dimethyl arsenate, trimethyl arsenous acid, fat-soluble arsenic and the like in antarctic krill.
Therefore, a method for effectively removing heavy metals in food, especially organic arsenic in an antarctic krill extract, is needed to be invented so as to ensure the safety of the food.
Disclosure of Invention
In order to solve the technical problems, the invention provides a treatment method for dearsenifying the euphausia superba extract, which is used for respectively treating the euphausia superba oil and the euphausia superba peptide powder obtained by different methods, and results show that the method disclosed by the invention is used for removing arsenic in the euphausia superba extract, the effect is excellent, and the arsenic content in the euphausia superba oil and the euphausia superba peptide powder after dearsenifying treatment is far less than 1ppm.
In addition, the invention also provides application of the adsorbent used in the method in removing total arsenic in the Antarctic krill extract.
The adsorbent has a structure shown in a general formula I in a publication number CN110191911A, and specific structures of the adsorbent are not described in detail since the patent is already disclosed.
The invention provides a processing method for dearsenization of an antarctic krill extract, which is mainly aimed at antarctic krill peptide powder and antarctic krill oil; when the Antarctic krill extract is Antarctic krill peptide powder, the dearsenization treatment steps are as follows:
(1) Dispersing the euphausia superba peptide powder in water or an acid solution to obtain a mixed solution I;
(2) Mixing the mixed solution I with an adsorbent to perform dearsenification treatment, and removing the adsorbent to obtain a mixed solution II;
(3) Carrying out desolventizing treatment on the mixed solution II to obtain dearsenified antarctic krill peptide powder;
when the Antarctic krill extract is Antarctic krill oil, the dearsenization treatment steps are as follows:
(1) Dissolving antarctic krill oil in an organic solvent to obtain a mixed solution A;
(2) And mixing the mixed solution A with an adsorbent, refluxing and stirring, performing rotary evaporation, and filtering to obtain the dearsenified antarctic krill oil.
The acid solution is either a hydrochloric acid solution or a phosphoric acid solution.
The organic solvent is ethanol solution or absolute ethanol.
The dearsenization treatment of the antarctic krill peptide powder comprises the following steps:
s1: removing shell of krill, washing krill meat, soaking, and draining;
s2: taking the drained krill in the S1, cutting into paste, heating or cooking, adding water, performing enzymolysis, and inactivating enzyme to obtain an enzymolysis solution;
s3: centrifugally separating the enzymolysis liquid in the S2, taking supernatant, and performing spray drying or freeze drying to obtain krill protein peptide;
s4: dissolving krill protein peptide in water or acid solution, wherein the weight ratio of krill protein peptide to water or acid solution is 1:1 to 100;
s5: adding an adsorbent according to the proportion of 0.5-50 wt% of the krill protein peptide, refluxing and stirring at 0-100 ℃ for 0.25-12 h, and filtering;
s6: and (3) drying to obtain antarctic krill peptide powder with arsenic content less than 1ppm, wherein the drying mode is as follows: any of vacuum drying, freeze drying or spray drying.
Preferably, in the step S2, the mixture is heated or steamed at the temperature of 95-100 ℃ for 6-20 min;
the weight ratio of the pasty phosphate shrimp meat to water is 1:6 to 10;
the enzyme adopted by enzymolysis is any one of neutral protease, alkaline protease and papain; the dosage of the enzyme is 2-5% of the weight of the Antarctic krill meat; the enzymolysis temperature is 40-55 ℃; inactivating enzyme at 90-98 deg.c for 5-15 min after enzymolysis;
the centrifugal speed is 2000-3000 rpm, and the centrifugal time is 5-10 min.
Preferably, S4: dissolving krill protein peptide in water or acid solution, wherein the weight ratio of krill protein peptide to water or acid solution is 1:1 to 90;
s5: adding an adsorbent according to the proportion of 0.5-45 wt% of the krill protein peptide, refluxing and stirring for 0.25-10 h at 40-90 ℃, and filtering.
The arsenic removal treatment of the Antarctic krill oil comprises the following steps:
s1: removing shell of krill, collecting krill meat, and washing;
s2: taking the cleaned krill meat in the S1, cooking, and centrifuging to remove water;
s3: drying and crushing the cooked krill to obtain krill meal;
s4: adding an organic solvent into the krill meal in the S3 to extract krill oil, stirring and extracting, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution to obtain the krill oil;
s5: and (3) dissolving the krill oil in the S4 in ethanol or absolute ethanol, adding an adsorbent, refluxing and stirring, performing rotary evaporation, and filtering to obtain the antarctic krill oil with the arsenic content of less than 1ppm.
The arsenic removal treatment of the Antarctic krill oil comprises the following steps:
s1: removing shell of krill, collecting krill meat, and washing;
s2: taking the cleaned krill meat in the S1, cooking at 90-105 ℃ for 10-20 min, and centrifuging at the rotating speed of 90-110 rpm for 3-7 min;
s3: drying the krill cooked in the S2 until the water content of the krill is less than 2%, and crushing by using a crusher to obtain krill powder;
s4: adding absolute ethyl alcohol into the krill meal in the S3 to extract krill oil, stirring and extracting for about 3 hours, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution at the temperature of 50-65 ℃ to obtain the krill oil;
s5: removing arsenic:
(1) Taking the krill oil in the S4, and mixing the krill oil with absolute ethyl alcohol 1: 3-6, adding absolute ethyl alcohol, fully dissolving at 50-68 ℃, and uniformly mixing to prepare an ethanol mixed solution of antarctic krill oil;
(2) Adding an adsorbent into the Antarctic krill oil ethanol mixed solution, adjusting the temperature to be 60-90 ℃, and performing reflux stirring for 1.5-5 h to perform dearsenization treatment;
(3) Filtering to remove the adsorbent in the treatment liquid, putting the filtrate into a vacuum drying oven for drying for 22-26 h at the temperature of 50-70 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
or, S1: preparing crude shrimp sauce:
(1) Cleaning Antarctic krill, shelling, crushing shrimp meat, adding distilled water to adjust the ratio of material to liquid to be 1:3 to 5;
(2) Adjusting the pH value of the material obtained in the step (1) to 7.4-7.8, adjusting the temperature to 40-55 ℃, adding alkaline protease for enzymolysis for 20-40 min, wherein the dosage of the alkaline protease is 3% of the weight of the shrimp meat;
(3) Adjusting the pH value to 6.3-6.7, adding papain, wherein the dosage of the papain is 3 percent of the weight of the shrimp meat, carrying out enzymolysis for 20-40 min again, and inactivating the enzyme for 8-12 min at 90-98 ℃;
(4) Adding 8-15 wt% of petroleum ether into the enzymolysis liquid in the step (2) for extraction for 20-40 min, and then centrifuging for 10-30 min at the rotating speed of 4000-6000 rpm to obtain 4 layers of materials, wherein the upper layer is an organic layer, the second layer is a grease emulsifying layer, the third layer is protein hydrolysis liquid, and the lowest layer is a very small amount of impurity layers such as shrimp shells;
(5) Collecting an organic layer and a grease emulsifying layer, adding petroleum ether into the grease emulsifying layer for extraction, centrifuging to obtain an organic layer, combining the organic layer in the step (4) and the organic layer obtained in the step (5), and performing rotary evaporation to remove the petroleum ether to obtain crude shrimp sauce;
s2: dearsenicating Antarctic krill oil
(6) Dissolving krill shrimp sauce in ethyl acetate;
(7) Adding an adsorbent, stirring to mix uniformly, standing, refluxing and stirring for 3-5 h, and performing dearsenification treatment;
(8) Filtering to remove the adsorbent in the treatment liquid, putting the filtrate into a vacuum drying oven for drying for 20-26 h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain the arsenic-removed euphausia superba oil.
The application of the structure of the adsorbent with the general formula I in the removal of arsenic in the Antarctic krill extract is also the important protection content of the invention, and the adsorbent is actually a targeted silica gel adsorption material.
According to the method, heavy metal arsenic in food (particularly the antarctic krill extract) is removed, the used principle is actually adsorption, in the adsorption process, the adsorbent with a specific structure and a general formula is adopted, and the silica gel material can convert the original antarctic krill extract containing arsenic into the dearsenic antarctic krill extract containing arsenic of 1mg/kg or less, so that the content of arsenic in the antarctic krill extract is greatly reduced, and the safety of food is remarkably improved.
The method disclosed by the invention is simple and convenient to operate, the used reagent is easy to obtain, the adsorption cost is low, the effect is excellent, the problem about total arsenic removal in the food industry is solved, and the method takes the removal of arsenic in the euphausia superba extract as an example, so that the excellent removal effect is obtained.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
Example 1
The adsorbent was prepared by the specific procedure of example 37 of published patent application CN110191911 a.
The adsorbent in example 1 is used as an adsorbent and applied to removal of arsenic in antarctic krill oil, and specific removal effects are shown in example 1.1:
example 1.1
Removing arsenic in antarctic krill oil, comprising the following steps:
s1: shelling Euphausia superba, taking Phosphous krill meat, and washing;
s2: taking the cleaned krill meat in the S1, cooking at 100 ℃ for about 15min, and centrifuging at the rotating speed of 100rpm for 5min so as to remove water in the krill meat;
s3: drying the euphausia superba cooked in the step S2 until the water content of the euphausia superba is less than 2%, and crushing the euphausia superba by using a crusher to obtain euphausia superba powder;
s4: adding absolute ethyl alcohol into the antarctic krill powder in the S3 to extract krill oil, stirring and extracting for about 3 hours, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution at 55 ℃ to obtain krill oil;
s5: removing arsenic:
(1) Taking 30g of krill oil in S4, adding anhydrous ethanol according to the weight ratio of the krill oil to the anhydrous ethanol 1:5, fully dissolving at 65 ℃, and uniformly mixing to prepare an ethanol mixed solution of the euphausia superba oil;
(2) Adding 5g of the adsorbent in the example 1 into the Antarctic krill oil ethanol mixed solution, adjusting the temperature to 80 ℃, and carrying out reflux stirring for 2 hours to carry out dearsenification treatment;
(3) Filtering to remove the adsorbent in the treatment liquid, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain the dearsenified antarctic krill oil;
(4) Sampling the total arsenic was determined by reference to the first second method of GB 5009.11-2014.
It is needless to say that the arsenic in the krill oil can be removed by using commercially available krill oil as an object by the above method without affecting the removal effect. That is, the process of the present invention is applicable not only to homemade krill oil, but also to commercially available krill oil, such as example 1.2.
Similarly, if the method is not adopted, the fresh krill meat is directly taken as the object, the object is cooked and then pasted, and the anhydrous ethanol is directly added to extract the krill oil, so that the same effect can be achieved. For example:
s2: taking the cleaned Antarctic krill meat in the step S1, cooking at 100 ℃ for about 15min, and centrifuging at the rotating speed of 100rpm for 5min so as to remove water in the Antarctic krill meat;
s3: beating the euphausia superba cooked in the step S2 into paste;
s4: and (3) adding absolute ethyl alcohol into the antarctic krill paste in the S3 to extract the krill oil, stirring and extracting for about 3 hours, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution at 55 ℃ to obtain the antarctic krill oil.
The krill oil obtained by the above method may be subjected to arsenic removal by the above process in S5.
Example 1.2
The adsorbent in example 1 was used as an adsorbent for removing arsenic from antarctic krill oil produced by Shandong company.
The specific application steps are as follows:
(1) Taking 10g of the Antarctic krill oil, adding absolute ethyl alcohol according to the weight ratio of the krill oil to the absolute ethyl alcohol 1:5, fully dissolving and uniformly mixing at 60 ℃ to prepare an Antarctic krill oil ethanol mixed solution;
(2) 5g of the adsorbent in the example 1 is added into the Antarctic krill oil ethanol mixed solution, the temperature is adjusted to 65 ℃, and the mixture is refluxed and stirred for 4 hours to be subjected to dearsenization treatment;
(3) Filtering to remove the adsorbent in the treatment liquid, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain the dearsenified antarctic krill oil;
(4) Sampling the total arsenic was determined by reference to the first second method of GB 5009.11-2014.
Example 1.3
The adsorbent in example 1 was used as an adsorbent for removing arsenic from antarctic krill oil produced by a company of Hubei.
(1) Taking 50g of the antarctic krill oil, adding absolute ethanol according to the mass ratio of the antarctic krill oil to the absolute ethanol of 1:3, fully dissolving at 50 ℃, and uniformly mixing to prepare an antarctic krill oil ethanol mixed solution;
(2) 5g of the adsorbent in the example 1 is added into the Antarctic krill oil ethanol mixed solution, the temperature is adjusted to be 60 ℃, and the mixture is refluxed and stirred for 4 hours to be subjected to dearsenization treatment;
(3) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
(4) Sampling the total arsenic was determined by reference to the first second method of GB 5009.11-2014.
Example 1.4
The adsorbent in example 1 was used as an adsorbent for removing arsenic from antarctic krill oil produced by a company of Henan.
(1) Taking 50g of the Antarctic krill oil, adding absolute ethyl alcohol according to the mass ratio of the Antarctic krill oil to the absolute ethyl alcohol of 1:3, fully dissolving at 50 ℃, and uniformly mixing to prepare an Antarctic krill oil-ethanol mixed solution;
(2) 5g of the adsorbent in the example 1 is added into the Antarctic krill oil ethanol mixed solution, the temperature is adjusted to be 60 ℃, and the mixture is refluxed and stirred for 4 hours to be subjected to dearsenization treatment;
(3) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
(4) Sampling the total arsenic was determined by reference to the first second method of GB 5009.11-2014. The following examples were all measured by this method.
The above experiments fully demonstrate that the targeted adsorption material in example 1 has an excellent effect on adsorbing arsenic in the Euphausia superba extract, and the content of arsenic is less than 1mg/kg after adsorption by the above method.
From examples 1.1 to 1.4, it can be seen that the method of the present invention can remove arsenic from krill oil, both from the home-made krill oil and from the commercial krill oil products, with a significant effect, and the arsenic content therein can be reduced to 1mg/kg.
Example 2.1
The targeted adsorption material in example 1 is applied to the dearsenification treatment of krill protein peptide powder, the application examples are shown in examples 2.1, 2.2, 2.3 and 2.4, and the specific steps are as follows:
taking a self-made krill protein peptide powder as an example, the method for dearsenizing the krill protein peptide powder comprises the following steps:
s1: removing shells of krill taken from Bohai sea, taking krill meat, washing, fully soaking, and draining water;
s2: taking the drained krill in the S1, cutting, pulping, cooking at 100 ℃ for 10 minutes, airing to about 50 ℃, adjusting the pH to about 7.0, performing enzymolysis (neutral protease, the enzyme addition amount is 3 percent of the weight of the krill) for 40min, and performing enzyme deactivation at 95 ℃ for 5min to obtain an enzymolysis solution;
s3: centrifuging the enzymolysis liquid in the S2, taking supernatant, and performing spray drying to obtain krill protein peptide;
s4: taking 30g of krill protein peptide, dissolving the krill protein peptide in 20wt% phosphoric acid solution to reach a constant volume of 100ml;
s5: 5g of the adsorbent in the example 1 is added, reflux stirring is carried out for 2h at 80 ℃, the mixture is filtered after being cooled to room temperature, the filtrate is freeze-dried for 24h, antarctic krill peptide powder is obtained, and sampling is carried out to detect total arsenic.
Example 2.2
The krill protein peptide powder dearsenization treatment method comprises the following steps:
s1: removing shell of krill from yellow sea, washing krill meat, soaking, and draining water;
s2: taking the drained krill in the S1, cutting, pulping, cooking at 100 ℃ for 10 minutes, airing to about 50 ℃, performing enzymolysis (adjusting the pH to about 7.8, adding alkaline protease, and inactivating the enzyme for 5 minutes at 95 ℃) to obtain an enzymolysis solution;
s3: centrifugally separating the enzymolysis liquid in the S2, taking supernatant, and freeze-drying to obtain krill protein peptide;
s4: taking 30g of krill protein peptide, dissolving the krill protein peptide in 35wt% hydrochloric acid solution to reach a constant volume of 100ml;
s5: 5g of the adsorbent in the example 1 is added, reflux stirring is carried out for 4 hours at the temperature of 60 ℃, the mixture is filtered after being cooled to the room temperature, the filtrate is freeze-dried for 36 hours, antarctic krill peptide powder is obtained, and sampling is carried out to detect total arsenic.
Example 2.3
The adsorbent in example 1 is used as an adsorbent and applied to removal of arsenic in the peptide powder of Antarctic krill of a certain company in Jiangsu province on the market;
the specific dearsenification method comprises the following steps:
taking 10g of the antarctic krill peptide powder, dissolving with 50% phosphoric acid solution to a constant volume of 100ml, adding 2g of the adsorbent in the example 1, refluxing and stirring at 50 ℃ for 4h, cooling to room temperature, filtering, wherein the filter residue is the adsorbent adsorbing arsenic, the filtrate is an antarctic krill extract solution, putting the filtrate into a freeze dryer, drying for 48h, and sampling to measure the total arsenic.
Example 2.4
The adsorbent in example 1 is used as an adsorbent and applied to removal of arsenic in euphausia superba peptide powder of a certain company in Henan province on the market;
taking 20g of the antarctic krill peptide powder, dissolving the antarctic krill peptide powder with 15% hydrochloric acid solution to a constant volume of 100ml, adding 1g of the adsorbent in the example 1, refluxing and stirring at 60 ℃ for 4h, cooling to room temperature, filtering, wherein filter residue is the adsorbent adsorbing arsenic, filtrate is an antarctic krill extract solution, putting the filtrate into a freeze dryer to dry for 48h, and sampling to measure total arsenic according to the second method of GB 5009.11-2014.
From the applications in examples 2.1 to 2.4, the method of the present invention showed significant arsenic removal effects for both the krill protein peptides produced by the manufacture and the krill peptide powders available on the market.
Regarding the removal effect of arsenic in the above-described embodiment, it is expressed in the form of a table as follows:
TABLE 1 examples 1.1-2.4 dearsenification effect (mg/kg) of Euphausia superba oil/peptide powder
| Before removal | After being removed | Removal rate% | |
| Example 1.1 | 3.46 | 0.29 | 91.62 |
| Example 1.2 | 9.77 | 0.78 | 92.04 |
| Example 1.3 | 6.83 | 0.54 | 92.09 |
| Example 1.4 | 7.68 | 0.47 | 93.88 |
| Example 2.1 | 8.29 | 0.20 | 97.59 |
| Example 2.2 | 7.74 | 0.57 | 92.64 |
| Example 2.3 | 5.29 | 0.35 | 93.38 |
| Example 2.4 | 6.21 | 0.31 | 95.00 |
Note: before and after removal respectively refer to krill oil samples before and after dearsenification treatment by using the targeted adsorption material of the invention.
As can be seen from table 1, when the targeted silica gel material in example 1 is used to adsorb heavy metal arsenic in antarctic krill oil and antarctic krill peptide, the removal rate of arsenic is as high as 97.59% through detection, which indicates that the targeted adsorption material has an excellent removal effect on heavy metal arsenic.
Example 3
The adsorbent is prepared by the following specific preparation steps of published patent application CN110191911A, example 62.
The targeted adsorption material was applied to the dearsenification treatment of the antarctic krill oil in examples 1.1, 1.2, 1.3 and 1.4, which are denoted as examples 3.1, 3.2, 3.3 and 3.4, namely, in 3.1 to 3.4, the treatment method corresponds to the antarctic krill oil in examples 1.1 to 1.4 in sequence, and the specific treatment results are shown in table 2.
Example 4
The targeted adsorption material in example 3 was applied to the dearsenification treatment of the euphausia superba protein peptide powder in examples 2.1, 2.2, 2.3 and 2.4, which are denoted as examples 4.1, 4.2, 4.3 and 4.4, that is, in 4.1 to 4.4, the treatment method corresponds to the euphausia superba protein peptides in examples 2.1 to 2.4 in sequence, and the specific treatment results are shown in table 2.
Table 2 dearsenifying effect (mg/kg) of euphausia superba oil/peptide powder in examples 3.1 to 4.4
| Before removal | After being removed | Percent removal | |
| Example 3.1 | 3.46 | 0.31 | 91.04 |
| Example 3.2 | 9.77 | 0.69 | 92.93 |
| Example 3.3 | 6.83 | 0.50 | 92.67 |
| Example 3.4 | 7.68 | 0.53 | 93.09 |
| Example 4.1 | 8.29 | 0.19 | 97.71 |
| Example 4.2 | 7.74 | 0.61 | 92.12 |
| Example 4.3 | 5.29 | 0.38 | 92.82 |
| Example 4.4 | 6.21 | 0.34 | 94.52 |
From the above table, it can be seen that, after the targeted adsorption material is replaced, the arsenic removal effect is still excellent for the same sample, and the highest removal rate reaches 97.71%, which indicates that the targeted adsorption material provided by the invention has relatively ideal stability in adsorption effect.
Example 5
The specific preparation steps of the adsorbent are shown in published patent application CN110191911A, example 74:
the targeted silica gel material is used as an adsorbent and applied to removal of arsenic in antarctic krill oil, the preparation method of the krill oil in the embodiment 5 is different from that in the embodiment 1.1, double-enzyme enzymolysis is adopted, and the specific preparation steps are as follows;
antarctic krill oil prepared by an aqueous enzymatic method is used as an object for dearsenification treatment, and the dearsenification treatment method comprises the following steps:
s1: preparing crude shrimp sauce:
(1) Cleaning Antarctic krill, shelling, crushing shrimp meat, and adding distilled water to adjust the feed-liquid ratio to 1:4;
(2) Adjusting the pH value of the material obtained in the step (1) to about 7.8, adjusting the temperature to 45 ℃, and adding alkaline protease for enzymolysis for 30min, wherein the dosage of the alkaline protease is 3% of the weight of the phosphorized shrimp meat;
(3) Adjusting pH to about 6.5, adding papain (3 wt% of shrimp), performing enzymolysis for 30min, and inactivating enzyme at 95 deg.C for 10min;
(4) Adding 10% petroleum ether into the enzymatic hydrolysate in the step (3) for extraction for 30min, then centrifuging for 20min at the centrifugal rotation speed of 5000rpm to obtain 4 layers of materials, wherein the upper layer is an organic layer, the second layer is a grease emulsifying layer, the third layer is protein hydrolysate, and the lowest layer is a very small amount of impurity layers such as shrimp shells;
(5) Collecting the organic layer and the grease emulsifying layer, adding petroleum ether into the grease emulsifying layer for extraction, centrifuging to obtain an organic layer, combining the organic layer in the step (4) and the organic layer obtained in the step (5), and performing rotary evaporation to remove the petroleum ether to obtain crude shrimp sauce;
s2: (6) Dissolving krill shrimp sauce in ethyl acetate, and mixing well;
(7) Adding the adsorbent in the embodiment 5, stirring to uniformly mix, standing, refluxing and stirring for 4 hours, and performing dearsenification treatment;
(8) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
(9) Sampling to measure the total arsenic.
Example 6
The method comprises the following steps of taking self-made krill oil as an object for dearsenification treatment, taking a self-made method as an organic solvent extraction method, and taking the targeted adsorption material in example 5 as an adsorbent:
s1: preparation of Antarctic krill oil
(1) Crushing fresh antarctic krill serving as a raw material, taking 95wt% ethanol as an extraction solvent, and mixing the raw material with the weight ratio of 1:10 at 45 ℃, performing suction filtration, transferring the extract after suction filtration to a rotary evaporator for rotary evaporation, and mixing the crude shrimp sauce according to the weight ratio of 1:4, adding absolute ethyl alcohol for redissolving, centrifuging to remove impurities, and then performing rotary evaporation to collect krill oil;
s2: dearsenification treatment
(2) Dissolving krill oil in 90wt% ethyl acetate, and mixing;
(3) Adding the adsorbent in the embodiment 5, stirring to uniformly mix, standing, refluxing and stirring for 4 hours, and performing dearsenification treatment;
(4) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
(5) Sampling to measure the total arsenic.
Example 7
The adsorbent in example 5 is used as an adsorbent and applied to dearsenification treatment of antarctic krill oil extracted from shrimp meal, and the specific application method is as follows:
s1: preparation of Antarctic krill oil
(1) Taking shrimp meal of fresh antarctic krill as a raw material, smashing, extracting for 3 hours at 55 ℃ by using 95% ethanol as an extraction solvent and using a feed-liquid ratio of 1:8, carrying out suction filtration, transferring an extracting solution after suction filtration to a rotary evaporator for rotary evaporation, adding absolute ethanol into crude krill oil according to 1:4 for redissolution, centrifuging to remove impurities, and then carrying out rotary evaporation to collect krill oil.
S2: performing dearsenification treatment on the antarctic krill oil prepared in the step S1:
(2) Dissolving krill shrimp sauce in absolute ethyl alcohol, and uniformly mixing;
(3) Adding the adsorbent in the embodiment 5, stirring to mix uniformly, standing, refluxing and stirring for 4 hours, and performing dearsenication treatment;
(4) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven for drying for 24h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
(5) Sampling to measure the total arsenic.
Example 8
The adsorbent in example 5 was used as an adsorbent and applied to dearsenization of antarctic krill oil produced by a company in Zhejiang province, and detection showed that the antarctic krill oil contained 6.83mg/kg arsenic, 2g of the antarctic krill oil was dissolved in 15% ethyl acetate to a constant volume of 100ml, 1g of the adsorbent in example 5 was added, the mixture was refluxed and stirred at 60 ℃ for 4 hours, and distilled under reduced pressure (the method was the same as in example 5), and a sample was taken to measure the total arsenic.
From examples 5 to 8, it can be seen that the method and the adsorbent of the present invention have excellent effects on the removal of arsenic from krill oil produced in different regions, and the content of arsenic in krill oil is reduced to less than 1mg/kg after treatment, which is within the range of food safety.
TABLE 3 Effect of arsenic removal for samples of examples 5 to 8
| Before removal | After being removed | Removal rate% | |
| Example 5 | 7.52 | 0.13 | 98.27 |
| Example 6 | 8.95 | 0.44 | 95.08 |
| Example 7 | 10.38 | 0.32 | 96.91 |
| Example 8 | 6.83 | 0.22 | 96.78 |
In the invention, experiments for removing arsenic in the antarctic krill extract by adsorption are selectively carried out on the adsorbents in the examples 1, 3 and 5, but the invention protects a technical scheme that the compounds with the structure of the general formula I in CN110191911A are applied to the removal of arsenic. Structures not recited in the present disclosure are not intended to represent a departure from the scope of the present disclosure.
The data in the above examples show that the targeted adsorption material of the invention has excellent effect when applied to the removal treatment of total arsenic in antarctic krill oil and antarctic krill peptide, the removal rate of the total arsenic can reach about 98.27% at most, and the targeted adsorption material of the same kind is applied to samples prepared by different methods, and shows stability in effect.
Claims (9)
1. A treatment method for dearsenifying an Antarctic krill extract is characterized by comprising the following steps:
when the Antarctic krill extract is Antarctic krill peptide powder, the dearsenization treatment steps are as follows:
(1) Dispersing the euphausia superba peptide powder in water or an acid solution to obtain a mixed solution I;
(2) Mixing the mixed solution I with an adsorbent for dearsenification treatment, wherein the treatment steps are as follows: adding an adsorbent according to the proportion of 0.5-45wt% of the krill protein peptide powder, stirring under reflux at 40-90 ℃ for 0.25-10h, filtering, and removing the adsorbent to obtain a mixed solution II;
the adsorbent is prepared by the methods of examples 37 and 62 in the patent application specification with the publication number of CN 110191911A;
(3) Carrying out desolventizing treatment on the mixed solution II to obtain dearsenified antarctic krill peptide powder;
when the Antarctic krill extract is Antarctic krill oil, the dearsenization treatment steps are as follows:
(1) Dissolving antarctic krill oil in an organic solvent to obtain a mixed solution A;
(2) Mixing the mixed solution A with an adsorbent, refluxing and stirring, performing rotary evaporation, and filtering to obtain dearsenified antarctic krill oil;
the adsorbent is prepared by the method of example 37, 62 or 74 in the patent application specification with the publication number of CN 110191911A.
2. The method for dearsenifying Euphausia superba extract according to claim 1, wherein said acid solution is either hydrochloric acid or phosphoric acid.
3. The method for dearsenifying an antarctic krill extract according to claim 1, wherein the organic solvent is one of absolute ethanol or ethyl acetate.
4. The method for dearsenicating Euphausia superba extract according to claim 2, wherein the dearsenicating treatment of Euphausia superba peptide powder comprises the following steps:
s1: removing shell of krill, washing krill meat, soaking, and draining;
s2: taking the drained krill in the S1, cutting into paste, heating or cooking, adding water, performing enzymolysis, and inactivating enzyme to obtain an enzymolysis solution;
s3: centrifuging the enzymolysis liquid in the S2, taking supernatant, and performing spray drying or freeze drying to obtain krill protein peptide powder;
s4: dissolving krill protein peptide powder in water or an acid solution, wherein the weight ratio of the krill protein peptide powder to the water or the acid solution is 1:1 to 100;
s5: adding an adsorbent according to the proportion of 0.5-45wt% of the krill protein peptide powder, stirring under reflux at 40-90 ℃ for 0.25-10 h, and filtering;
s6: and (3) drying to obtain antarctic krill peptide powder with the arsenic content of less than 1ppm, wherein the drying mode is as follows: any of vacuum drying, freeze drying or spray drying.
5. The method for dearsenifying Euphausia superba extract as claimed in claim 4, wherein S2 is heated or cooked at 95-100 deg.C for 6-20min;
the weight ratio of the pasty phosphorus shrimp meat to water is 1:6 to 10;
the enzyme adopted by enzymolysis is any one of neutral protease, alkaline protease and papain; the dosage of the enzyme is 2~5% of the weight of the krill meat; the enzymolysis temperature is 40 to 55 ℃; after enzymolysis, enzyme is inactivated for 5 to 15min at the temperature of 90 to 98 ℃;
and in S3, the centrifugal rotation speed is 2000-3000 rpm, and the centrifugal time is 5-10min.
6. The treatment method for dearsenifying Euphausia superba extract according to claim 4, wherein S4: dissolving krill protein peptide powder in water or an acid solution, wherein the weight ratio of the krill protein peptide powder to the water or the acid solution is 1:1 to 90.
7. The method for dearsenicating Euphausia superba extract according to claim 1, wherein the dearsenicating treatment of Euphausia superba oil comprises the following steps:
s1: removing shell of krill, collecting krill meat, and washing;
s2: taking the cleaned krill meat in the S1, cooking, and centrifuging to remove water;
s3: drying and crushing the cooked krill to obtain krill meal;
s4: adding an organic solvent into the krill meal in the S3 to extract krill oil, stirring and extracting, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution to obtain the krill oil;
s5: and (3) dissolving the krill oil in the S4 in absolute ethyl alcohol, adding an adsorbent, refluxing and stirring, performing rotary evaporation, and filtering to obtain the antarctic krill oil with the arsenic content of less than 1ppm.
8. A treatment method for dearsenifying antarctic krill oil is characterized by comprising the following steps:
s1: removing shell of krill, collecting krill meat, and washing;
s2: taking the phosphate shrimp meat washed clean in the S1, cooking at 90-105 ℃ for 10-20min, and centrifuging at the rotation speed of 90-110rpm for 3-7min;
s3: drying the krill cooked in the step S2 until the water content of the krill is less than 2%, and crushing the krill by using a crusher to obtain krill powder;
s4: adding absolute ethyl alcohol into the krill meal in the S3 to extract krill oil, stirring and extracting for 3 hours, filtering to obtain an extracting solution, and performing rotary evaporation on the extracting solution at 50-65 ℃ to obtain the krill oil;
s5: removing arsenic:
(1) Taking the krill oil in the S4, and mixing the krill oil with absolute ethyl alcohol 1: 5363 adding anhydrous ethanol into 3~6, dissolving at 50-68 deg.C, and mixing to obtain mixed solution;
(2) Adding an adsorbent into the Antarctic krill oil ethanol mixed solution, adjusting the temperature to be 60 to 90 ℃, and carrying out arsenic removal treatment by refluxing and stirring for 1.5 to 5 hours; the adsorbent is prepared by the method of example 37 or 62 in the patent application specification with the publication number of CN 110191911A;
(3) Filtering to remove the adsorbent in the treatment liquid, putting the filtrate into a vacuum drying oven for drying for 22 to 26h at the temperature of 50 to 70 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and distilling under reduced pressure for desolventizing to obtain the arsenic-removed antarctic krill oil;
or, S1: preparing crude shrimp sauce:
(1) Cleaning Antarctic krill, shelling, crushing shrimp meat, adding distilled water to adjust the ratio of material to liquid to be 1:3~5;
(2) Adjusting the pH value of the material obtained in the step (1) to 7.4-7.8, adjusting the temperature to 40-55 ℃, adding alkaline protease for enzymolysis for 20-40min, wherein the dosage of the alkaline protease is 3% of the weight of the shrimp meat;
(3) Adjusting the pH value to 6.3 to 6.7, adding papain, wherein the dosage of the papain is 3 percent of the weight of the shrimp meat, carrying out enzymolysis for 20 to 40min again, and inactivating the enzyme for 8 to 12min at 90 to 98 ℃;
(4) Adding 8-15wt% petroleum ether into the enzymolysis liquid in the step (3) to extract for 20-40min, and then centrifuging for 10-30min at the rotating speed of 4000-6000 rpm to obtain a 4-layer material, wherein the upper layer is an organic layer, the second layer is an oil emulsifying layer, the third layer is protein hydrolysis liquid, and the lowest layer is a very small amount of impurity layers including shrimp shells;
(5) Collecting an organic layer and a grease emulsifying layer, adding petroleum ether into the grease emulsifying layer for extraction, centrifuging to obtain an organic layer, combining the organic layer collected in the step (4) and the organic layer obtained in the step (5), and performing rotary evaporation to remove the petroleum ether to obtain crude shrimp sauce;
s2: dearsenization treatment of Antarctic krill oil
(6) Dissolving the crude shrimp sauce in ethyl acetate;
(7) Adding an adsorbent, stirring to mix uniformly, standing, refluxing and stirring for 3 to 5 hours, and performing dearsenification treatment;
(8) Filtering to remove the adsorbent in the treatment solution, putting the filtrate into a vacuum drying oven, drying for 20 to 26h at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa, and performing reduced pressure distillation and desolventizing to obtain arsenic-removed euphausia superba oil;
the adsorbent was prepared by the method of example 74 in the specification of patent application publication No. CN110191911 a.
9. Use of the adsorbent as claimed in claim 1 for removing arsenic from an extract of Euphausia superba.
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