CN112126517B - Low-arsenic high-phospholipid process for improving initial shrimp oil quality - Google Patents
Low-arsenic high-phospholipid process for improving initial shrimp oil quality Download PDFInfo
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- CN112126517B CN112126517B CN202011064902.3A CN202011064902A CN112126517B CN 112126517 B CN112126517 B CN 112126517B CN 202011064902 A CN202011064902 A CN 202011064902A CN 112126517 B CN112126517 B CN 112126517B
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 241000238557 Decapoda Species 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 24
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000741 silica gel Substances 0.000 claims abstract description 41
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 41
- 239000003463 adsorbent Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000002798 polar solvent Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 235000015067 sauces Nutrition 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 16
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical group C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims 2
- 239000003921 oil Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 16
- 150000003904 phospholipids Chemical class 0.000 abstract description 8
- 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 abstract description 7
- 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 abstract description 7
- 229940022405 astaxanthin Drugs 0.000 abstract description 7
- 235000013793 astaxanthin Nutrition 0.000 abstract description 7
- 239000001168 astaxanthin Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 229940106134 krill oil Drugs 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 14
- 235000013305 food Nutrition 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 241000239370 Euphausia superba Species 0.000 description 4
- 241000239366 Euphausiacea Species 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 201000005569 Gout Diseases 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004641 brain development Effects 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application relates to a low-arsenic high-phospholipid process for improving the quality of initial shrimp oil. The method comprises the following steps: the first step, re-dissolving and filtering the initial shrimp oil for a plurality of times by using a certain volume of polar solvent, and removing the solvent to obtain a solution A; secondly, adding a certain volume of polar solvent into the solution A, and contacting with an adsorbent to carry out dearsenification treatment to obtain a mixed solution B, wherein the adsorbent is an iron-carrying silica gel material or an iron-carrying multifunctional silica gel material; and thirdly, desolventizing the mixed solution B to obtain the high-quality shrimp sauce. The process can remove toxic substances such as arsenic and insoluble impurities in the shrimp oil, has high oil yield and low loss rate of phospholipid and astaxanthin, and greatly improves the quality of the shrimp oil.
Description
Technical Field
The application relates to the field of foods, and relates to a low-arsenic high-phospholipid process for improving the quality of initial shrimp oil.
Background
The shrimp oil has rich active ingredients and contains phospholipids, astaxanthin, DHA, EPA and the like. Can be widely applied to industries such as food, health-care food, biological medicine and the like, and has higher deep development and application values. However, the extraction of shrimp oil has many technical problems at present. A typical antarctic krill oil is taken as an example for the development. The antarctic krill oil as a novel marine functional grease has attracted great research interests in various countries due to unique components and positive health care functions. The antarctic krill oil is a product with high nutrition efficacy and added value in antarctic krill related products. The main active components of the antarctic krill oil are phospholipid, astaxanthin, DHA, EPA and the like. Researches show that the antarctic krill oil has certain effects in preventing cardiovascular and cerebrovascular diseases, promoting brain development, resisting oxidization, relieving gout, rheumatoid arthritis and the like. Therefore, the antarctic krill oil can be widely applied to industries such as food, health-care food, biological medicine and the like, and has higher deep development and application values.
The method mainly comprises the steps of extracting euphausia superba oil in China, wherein euphausia superba powder is mainly used as a raw material, and an organic solvent method is mainly used. One-step or continuous countercurrent extraction process of antarctic krill oil with ethanol as extractant has been used in China. However, ethanol is miscible with water, and the krill powder still contains about 10% of water, and when ethanol is used as an extractant, a part of water-soluble impurities such as proteins, inorganic salts and the like are dissolved, so that the krill oil contains more impurities and is more viscous, and the quality of the krill oil is affected. The common oil refining process can damage the functional substances such as phospholipid, astaxanthin and the like in the antarctic krill oil, and is not suitable for refining the antarctic krill oil. The refining process applicable to antarctic krill oil is less studied at present and mainly aims at removing insoluble impurities, free fatty acids and other adverse substances. Thus, the euphausia superba oil extracted with ethanol needs to be further refined.
In addition, as people pay attention to antarctic ocean resources represented by antarctic krill, people also find that high concentrations of arsenic are contained in marine organisms such as antarctic krill and the like. Particularly arsenic enriched in krill oil is a critical issue for the antarctic krill oil industry.
The current academic method for removing arsenic in antarctic krill oil is basically in an exploration stage, and mainly aims at researching the occurrence form of arsenic in the krill oil, the migration direction of arsenic in processing and the like. As the national standard about the total arsenic content of aquatic products in foods is limited to a level below 1mg/kg, the total arsenic content in shrimp oil reaches about 4-10 mg/kg, which is far beyond the limit of the national standard; and the arsenic in the shrimp oil mainly exists in the form of organic arsenic, so that the arsenic is more difficult to remove, and even if the organic arsenic is detected, no corresponding national standard rule exists. In industry, some enterprises can reduce the total arsenic content in antarctic krill oil to 0.529mg/kg, but the corresponding oil yield is not more than 55%, and the loss rate of phospholipid is also more than 40%, which greatly influences the quality of the krill oil.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides a low-arsenic high-phospholipid process for improving the quality of initial shrimp oil.
A low-arsenic high-phospholipid process for improving the quality of initial shrimp oil comprises the following steps:
the first step, re-dissolving and filtering the initial shrimp oil for a plurality of times by using a certain volume of polar solvent, and removing the solvent to obtain a solution A;
secondly, adding a certain volume of polar solvent into the solution A, and contacting with an adsorbent to carry out dearsenification treatment to obtain a mixed solution B, wherein the adsorbent is an iron-carrying silica gel material or an iron-carrying multifunctional silica gel material;
and thirdly, desolventizing the mixed solution B to obtain the high-quality shrimp sauce C.
According to the scheme, the preparation method of the adsorbent comprises the following steps: reacting silica gel material or multifunctional silica gel material with ferric salt solution at 20-80deg.C for 0.5-48 hr, filtering, washing, and drying to obtain adsorbent.
According to the scheme, in the first step, the polar solvent is ethyl acetate, acetone, ethanol and water, one solvent is used for each re-dissolution or one different solvent is replaced for each time, and the re-dissolution frequency is more than or equal to 3.
According to the scheme, in the first step, the volume ratio of the initial shrimp paste to the polar solvent is 1:1-100, preferably 1:10-100.
According to the above scheme, the solvent is removed by rotary evaporation in the first step.
According to the scheme, in the second step, the polar solvent is ethanol and water.
According to the above scheme, in the second step, the volume ratio of the solution A to the polar solvent is 1:1-50, preferably 1:5-15.
According to the scheme, the dearsenification treatment is in a slurry mode and a fixed bed mode, wherein the slurry mode is to add an adsorbent into a system, stir and adsorb the adsorbent, and then filter the adsorbent; the fixed bed mode is as follows: fixing the adsorbent on a fixed bed or an adsorption column, and then enabling a system to be treated to flow through the chromatographic column with the fixed adsorbent for adsorption treatment, wherein the chromatographic columns are connected in series or in parallel.
According to the scheme, the silica gel raw material is mesoporous silica, and the silica gel is amorphous particles or spherical particles; the particle size of the silica gel is 10nm-30mm, and the pore size is 2-50nm.
According to the scheme, the preparation method of the adsorbent comprises the following steps: reacting silica gel material or multifunctional silica gel material with ferric salt solution at 20-80deg.C for 0.5-48 hr, filtering, washing, and drying to obtain adsorbent.
According to the scheme, in the third step, the solvent is removed by rotary evaporation, and the rotation temperature is 30-60 ℃.
According to the scheme, the multifunctional silica gel material iron-carrying adsorbent comprises the following components:
[[(O 3/2 )Si(CH 2 ) x T] m Fe n ] a [Si(O 4/2 )] b [(CH 2 ) u WSi(O 3/2 )] c [VSi(O 3/2 )] d I
t is selected from S (CH) 2 ) y NH(CH 2 CH 2 NH) z H,-NH(CH 2 CH 2 NH) z H is formed; a compound of formula II; p (=o) (OM) 2 ，P(＝O)H(OM)；S(CH 2 ) 3 SO 3 M；COOM，
Wherein: r is R 0 Is hydrogen, C 1-22 Alkyl or aryl; n is an integer from 0 to 100; l (L) 1 Is an anion including, but not limited to, halides, nitrates, sulfates, carbonates, phosphates, chromates, permanganates, borohydrides, substituted borohydrides such as cyano-substituted borohydrides; m is H, an alkali metal, an alkaline earth metal, wherein x is an integer from 2 to 12; y is an integer from 3 to 12; z is an integer from 0 to 100; u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, v is an integer from 2 to 6; v is selected from C 1-22 -alkyl, C 1-22 Alkylaryl, aryl, C 2-20 -alkyl sulfide radical, C 1-12 Alkyl, C 2-20 Alkylene thioether alkyl, C 2-20- Alkyl thioether aryl, C 2-20 -an alkylene thioether aryl group; a, b, c, d, m, n are integers and a+c+d: b is in a ratio of 0.000001 to 100, a and b are all present, and when c or d or both are greater than zero, the ratio of c+d to a+b is in a ratio of 0.000001 to 100; the ratio of m to n is 100-0.01.
According to the scheme, the multifunctional silica gel material is carriedIron adsorbent [ (O) 3/2 )Si(CH 2 ) x T] m Fe n ] a [Si(O 4/2 )] b [(CH 2 ) u WSi(O 3/2 )] c [VSi(O 3/2 )] d The preparation method of (2) comprises the following steps:
when T is S (CH) 2 ) y NH(CH 2 CH 2 NH) z H,-NH(CH 2 CH 2 NH) z H, the preparation method comprises the following steps: (1) (CH) 3 O) 3 Si(CH 2 ) x S(CH 2 ) y Cl or (CH) 3 O) 3 Si(CH 2 ) x Cl, x is an integer from 2 to 12, y is an integer from 3 to 12, and polyethylene polyamine NH 2 (CH 2 CH 2 NH) z H, z is 0-10, and the polyamine silane coupling agent is obtained through reflux reaction; (2) Then in solvent system and silica gel reflux reaction, polyamine silane coupling agent is loaded on silica gel, then sulfhydryl silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product A; (3) The product A reacts with ferric salt solution to obtain a Fe-loaded functionalized silica gel material A-Fe;
when T is a compound of formula II, the preparation thereof comprises the steps of: (1) (CH) 3 O) 3 Si(CH 2 ) n1 CH＝CH 2 N1 is an integer from 0 to 10, and reflux-reacting with silica gel in a solvent system, filtering, washing, drying, and then reacting with (CH) 2 CHCH 2 ) 2 N + (R 0 ) 2 L 1 Placing the mixture in a solvent, and adding a free radical initiator at 20-150 ℃ at fixed time to react for 10 minutes to 48 hours; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product B; (3) Combining product B with a solution of iron saltReacting to obtain a Fe-loaded functionalized silica gel material B-Fe;
when T is P (=O) (OM) 2 Or H 2 P (=o) (OM), the synthesis of which comprises the steps of: (1) ((CH) 3 O) 3 Si(CH 2 ) n1 CH＝CH 2 N1 is an integer from 0 to 10, and is reacted with silica gel in a solvent system under reflux, filtered, washed, dried and then reacted with HP (=O) (OM) 2 Or H 2 P (=O) (OM) is placed in a solvent, and a free radical initiator is added at a timing under the condition of 20-150 ℃ for reaction for 10 minutes to 48 hours; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product C; (3) The product C reacts with ferric salt solution to obtain a Fe-loaded functional silica gel material C-Fe;
when T is SO 3 M, its synthesis includes the following steps: (1) Respectively adding (CH) 3 O) 3 Si(CH 2 ) x SH and C3H6O3S (1, 3-propane sultone), x is an integer from 2 to 12, and adding triethylamine and ethanol to react for 0.5 to 12 hours at 20 to 150 ℃ for 10 minutes to 48 hours; cooling to room temperature, and dropwise adding the sulfuric acid solution into the reaction kettle for 0.5-12 h; adding silica gel to react for 10 minutes to 48 hours at the temperature of 20-150 ℃; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product D; (3) The product D reacts with ferric salt solution to obtain a Fe-loaded functionalized silica gel material D-Fe;
when T is COOM, the synthesis is characterized in that: the method comprises the following steps: (1) Respectively adding (CH) 3 O) 3 Si(CH 2 ) x SH and C4H2O3 (maleic anhydride), x is an integer from 2 to 12, and adding triethylamine and ethanol to the mixture for 0.5 to 12 hours at 20 to 150 ℃ for mixed solution reaction for 10 minutes to 48 hours; adding siliconContinuing the reaction of the glue at 20-150 ℃ for 10 minutes to 48 hours; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product E; (3) And (3) reacting the product E with an iron salt solution to obtain the Fe-carrying functionalized silica gel material E-Fe.
According to the scheme, the iron in the ferric salt solution is Fe 3+ Or iron complex anions exist, and the ferric salt solution is ferric sulfate, ferric chloride, ferric bromide, ferric nitrate, polymeric ferric chloride and polymeric ferric sulfate.
According to the scheme, the reaction temperature after adding the ferric salt solution in the step (3) is 20-80 ℃.
According to the scheme, the reaction time after the ferric salt solution is added in the step (3) is 0.5-48h.
The application has the beneficial effects that:
the process of the application uses the iron-carrying silica gel material or the iron-carrying multifunctional silica gel material adsorbent, is used for shrimp oil treatment, can remove toxic substances arsenic and insoluble impurities in the shrimp oil, has high oil yield, low loss rate of phospholipid and astaxanthin, total arsenic content of less than 0.1mg/kg, shrimp oil yield of more than or equal to 90%, loss rate of phospholipid and astaxanthin of less than or equal to 10%, and greatly improves the quality of the shrimp oil;
the dearsenifying step is simple and easy to operate, safe and nontoxic, the raw material of the adsorbent is food grade, and the adsorbent has the advantage of natural food safety
Detailed Description
The present application will be described in detail below with reference to specific examples for the purpose of facilitating understanding. It should be particularly pointed out that these descriptions are merely exemplary descriptions and do not constitute limitations on the scope of the application. Many variations and modifications of the application will be apparent to those skilled in the art in light of the teachings of this specification.
Example 1
Tetraethylenepentamine (6840 g,36 mol) and (CH) were added to a 50L reactor 3 O) 3 Si(CH 2 ) 3 S(CH 2 ) 3 Cl (24 mol) was stirred and heated at 130℃for 5 hours, then cooled to 70℃and ethanol (5000 mL) was added thereto and refluxed for 2 hours until the liquid became transparent, cooled and transferred to a 100L reactor, and heptane (40.0L) and silica gel (16.0 kg,37-500 μm,) The temperature of the oil bath is set at 130 ℃, and after the temperature of the oil bath reaches a set value, ethanol is collected, and the whole process lasts for 3 hours. 3-mercaptopropyl-trimethoxysilane (3436 mL,18 mol) was added and the mixture was heated for 5 hours and cooled. The liquid was removed and the solid was stirred with water (100L) for 30min and filtered. Further water (100L) was added to the solid and the mixture was stirred for 30min and filtered. This procedure was repeated 3 more times and dried to give a component of the formula I, wherein T is S (CH 2 ) y NH(CH 2 CH 2 NH) z H is formed; x is 3; y is 3 and z is 4; w is SH, u is 3, and d is 0. (noted as product A)
To 100ml of a 100ppm ferric chloride solution of 12M hydrochloric acid, 5g of the product A was added, and the mixture was stirred at 60℃for 6 hours, and then the mixture was filtered, washed and dried to obtain the product A-Fe.
Silica gel (37-500 μm,20 kg) and water (42L) were mixed with stirring at 100℃and vinyltrimethoxysilane (16 mol) was added thereto, and the reaction mixture was heated and stirred for 5 hours. After cooling, the solid was filtered, washed thoroughly with water and dried to give a vinyl silica gel solid. Phosphorous acid (3280 g,40 mol) and RO (10L) water were put into a 50L reaction vessel and stirring was started, the above vinyl silica gel (1.4-2.0 mmol/g,4.0 kg) was put into and tert-butyl hydroperoxide (40 ml) was added, stirring was continued for 40min at room temperature, heating was started, the temperature of the oil bath was set at 130 ℃, when the temperature of the oil bath reached and there was liquid reflux, tert-butyl hydroperoxide was added at 8ml per 15 min, the liquid was removed after cooling, and the solid was stirred for 30min with water (30L) and filtered. Further water (30L) was added to the solid and the mixture was stirred for 30min and filtered. Repeating the process for 3 times, and drying to obtainA component of formula i wherein T is P (=o) (OM) 2 and m is H; x is 3; the integer c is 0 and the integer d is 0. (noted as product C) to 100ml of 100ppm ferric sulfate solution was added 5g of product C, stirred at 60℃for 6 hours, and then filtered, washed and dried to obtain product C-Fe.
Example 2
(1) Adding food-grade absolute ethanol (volume ratio of 1:20) into initial Euphausia superba oil, stirring at 40deg.C for 10min-2h, filtering, washing, and evaporating solvent at 30-60deg.C by rotary evaporator. Repeating the above operation for 3-5 times to obtain solution A.
(2)
To 50g of the solution A, 500ml of food grade absolute ethanol was added, and after stirring until complete dissolution, 25g of the C-Fe adsorbent of example 2 was added, and stirring was carried out at 30℃for 4 hours, and then filtration was carried out with 200 mesh filter cloth, to obtain a mixed solution B2. Evaporating the mixed solution B2 to dry ethanol at 40 ℃ by using a rotary evaporator, washing the filter residue in the embodiment 6 by using the recovered ethanol, repeating the steps for three times, and evaporating the filtrate for the last time to obtain the high-quality shrimp sauce C1.
Or (b)
To 50g of the solution A, 500ml of food grade absolute ethyl alcohol was added, and after stirring until complete dissolution, 25g of the A-Fe adsorbent of example 2 was added, and stirring was carried out at 30℃for 4 hours, and then filtration was carried out with 200 mesh filter cloth, to obtain a mixed solution B3. Evaporating the mixed solution B2 to dry ethanol at 40 ℃ by using a rotary evaporator, washing the filter residue in the embodiment 6 by using the recovered ethanol, repeating the steps for three times, and evaporating the filtrate for the last time to obtain the high-quality shrimp sauce C2.
The mass, total arsenic, phospholipid, EPA, DHA and astaxanthin contents of the solutions C1 and C2 are detected according to a national standard method, and the characterization results are as follows:
-indicating undetected.
The above examples are provided for illustrating the technical concept and features of the present application and are intended to enable those skilled in the art to understand the contents of the present application and to implement the same, and are not intended to limit the scope of the present application. All equivalent changes or modifications made according to the spirit of the present application should be included in the scope of the present application.
Claims (12)
1. A low-arsenic high-phospholipid process for improving the quality of initial shrimp oil is characterized in that: the method comprises the following steps:
the first step, re-dissolving and filtering the initial shrimp oil for a plurality of times by using a certain volume of polar solvent, and removing the solvent to obtain a solution A;
secondly, adding a certain volume of polar solvent into the solution A, and contacting with an adsorbent to carry out dearsenification treatment to obtain a mixed solution B;
thirdly, desolventizing the mixed solution B to obtain high-quality shrimp sauce;
the adsorbent is an iron-carrying multifunctional silica gel material;
the iron-carrying multifunctional silica gel material adsorbent is as follows: [ [ (O) 3/2 )Si(CH 2 ) x T] m Fe n ] a [Si(O 4/2 )] b [(CH 2 ) u WSi(O 3/2 )] c [VSi(O 3/2 )] d
T is selected from S (CH) 2 ) y NH(CH 2 CH 2 NH) z H、-NH(CH 2 CH 2 NH) z H. Compounds of general formula II, P (=O) (OM) 2 Or P (=o) H (OM);
wherein: r is R 0 Is hydrogen, C 1-22 Alkyl or aryl;
n is an integer from 0 to 100, n being other than 0;
L 1 is an anion selected from the group consisting of halides, nitrates, sulfates, carbonates, phosphates, chromates, permanganates, borohydrides, substituted borohydrides;
m is H, an alkali metal or an alkaline earth metal;
x is an integer from 2 to 12;
y is an integer from 3 to 12;
z is an integer from 0 to 100;
u is an integer from 2 to 12;
w is SH or S (CH) 2 ) v SH, v is an integer from 2 to 6;
v is selected from C 1-22 -alkyl, C 1-22 Alkylaryl, aryl, C 2-20 -alkyl sulfide radical, C 2-20 Alkylene thioether alkyl, C 2-20 -alkyl thioether aryl, C 2-20 -an alkylene thioether aryl group;
a, b, c, d, m, n are integers and a+c+d: b is in a ratio of 0.000001 to 100, a and b are all present, and when c or d or both are greater than zero, the ratio of c+d to a+b is in a ratio of 0.000001 to 100; the ratio of m to n is 100-0.01;
the dearsenification treatment adopts a slurry mode or a fixed bed mode;
the slurry mode is to add the adsorbent into a solution A system added with a polar solvent, stir and adsorb the adsorbent, and then filter the adsorbent;
the fixed bed mode is as follows: fixing an adsorbent on a fixed bed or an adsorption column, then enabling a solution A system to be treated, added with a polar solvent, to flow through the fixed bed or the adsorption column, on which the adsorbent is fixed, for adsorption treatment, wherein the adsorption columns are connected in series or in parallel;
the polar solvent used in the first step is ethyl acetate, acetone, ethanol or water;
the polar solvent used in the second step is ethanol or water.
2. The process according to claim 1, characterized in that: in the first step, one solvent is used for each redissolution or a different solvent is replaced each time, and the redissolution frequency is more than or equal to 3.
3. The process according to claim 1, characterized in that: in the first step, the volume ratio of the initial shrimp paste to the polar solvent is 1:1-100.
4. The process according to claim 1, characterized in that: in the first step, the volume ratio of the initial shrimp paste to the polar solvent is 1:10-100.
5. The process according to claim 1, characterized in that: in the second step, the volume ratio of the solution A to the polar solvent is 1:1-50.
6. The process according to claim 1, characterized in that: in the second step, the volume ratio of the solution A to the polar solvent is 1:1-15.
7. The process according to claim 1, characterized in that: in the third step, the solvent is removed by rotary evaporation, and the rotation temperature is 30-60 ℃.
8. The process according to claim 1, characterized in that: the silica gel raw material in the iron-carrying multifunctional silica gel material is mesoporous silica, and the silica gel is amorphous particles or spherical particles; the particle size of the silica gel is 10nm-30mm, and the pore size is 2-50nm.
9. The process according to claim 1, characterized in that: iron-carrying multifunctional silica gel material adsorbent [ [ (O) 3/2 )Si(CH 2 ) x T] m Fe n ] a [Si(O 4/2 )] b [(CH 2 ) u WSi(O 3/2 )] c [VSi(O 3/2 )] d The preparation method of (2) comprises the following steps:
when T is S (CH) 2 ) y NH(CH 2 CH 2 NH) z H or-NH (CH) 2 CH 2 NH) z In the case of H, the preparation method comprises the following steps: (1) (CH) 3 O) 3 Si(CH 2 ) x S(CH 2 ) y Cl or (CH) 3 O) 3 Si(CH 2 ) x Cl, x is an integer from 2 to 12, y is an integer from 3 to 12, and polyethylene polyamine NH 2 (CH 2 CH 2 NH) z H, z is 0-10, and the polyamine silane coupling agent is obtained through reflux reaction; (2) Silicon is then neutralized in a solvent systemThe reaction of the gel is carried out by the back flow, the polyamine silane coupling agent is loaded on the silica gel, and then the sulfhydryl silane coupling agent (CH 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product A; (3) The product A reacts with ferric salt solution to obtain a Fe-carrying silica gel material A-Fe;
when T is a compound of formula II, the preparation thereof comprises the steps of: (1) (CH) 3 O) 3 Si(CH 2 ) n1 CH＝CH 2 ,n 1 Is an integer from 0 to 10, is reacted with silica gel in a solvent system under reflux, filtered, washed, dried and then reacted with (CH) 2 CHCH 2 ) 2 N + (R 0 ) 2 L 1 Placing the mixture in a solvent, and adding a free radical initiator at 20-150 ℃ at fixed time to react for 10 minutes to 48 hours; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product B; (3) The product B reacts with ferric salt solution to obtain a Fe-carrying functional silica gel material B-Fe;
when T is P (=O) (OM) 2 Or P (=o) H (OM), the synthesis of which comprises the steps of: (1) ((CH) 3 O) 3 Si(CH 2 ) n1 CH＝CH 2 N1 is an integer from 0 to 10, and is reacted with silica gel in a solvent system under reflux, filtered, washed, dried and then reacted with HP (=O) (OM) 2 Or H 2 P (=O) (OM) is placed in a solvent, and a free radical initiator is added at a timing under the condition of 20-150 ℃ for reaction for 10 minutes to 48 hours; (2) Then adding mercapto silane coupling agent (CH) 3 O) 3 Si(CH 2 ) u W, u is an integer from 2 to 12; w is SH or S (CH) 2 ) v SH, continuing reflux reaction, loading mercaptosilane coupling agent, and finally adding VSi (O) 3/2 ) Reflux reaction to obtain a product C; (3) The product C reacts with ferric salt solution to obtain the Fe-carrying functionSilica gel material C-Fe.
10. The process according to claim 9, characterized in that: the reaction temperature after adding the ferric salt solution in the step (3) is 20-80 ℃ and the reaction time is 0.5-48h.
11. The process according to claim 10, wherein: the iron in the ferric salt solution is Fe 3+ Or in the form of iron complex anions.
12. The process according to claim 11, wherein: the ferric salt solution is ferric sulfate, ferric chloride, ferric bromide, ferric nitrate, polymeric ferric chloride or polymeric ferric sulfate.
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