阅读说明：本技术 一种脱除南极磷虾油中砷的方法 (Method for removing arsenic in euphausia superba oil ) 是由 曲有乐 欧阳小琨 卢雨清 杨立业 郁迪 于 2019-10-10 设计创作，主要内容包括：本发明涉及水产品加工技术领域,为解决传统脱除南极磷虾油中砷的方法复杂、吸附剂不易脱除的问题,提供了一种脱除南极磷虾油中砷的方法,将南极磷虾油分散于有机溶剂中,加入EDTA接枝磁性壳聚糖,超声震荡反应后,去除EDTA接枝磁性壳聚糖,得到去除砷后的南极磷虾油。本发明利用EDTA接枝的磁性壳聚糖微球高效吸附脱除南极磷虾油中的砷,此材料具有环境友好,易分离,可持续使用等优点；脱除砷后的南极磷虾油可以拓展其应用,增强其安全性。(The invention relates to the technical field of aquatic product processing, and provides a method for removing arsenic from antarctic krill oil, aiming at solving the problems that the traditional method for removing arsenic from antarctic krill oil is complex and an adsorbent is not easy to remove. According to the invention, the EDTA grafted magnetic chitosan microspheres are used for efficiently adsorbing and removing arsenic in the antarctic krill oil, and the material has the advantages of environmental friendliness, easiness in separation, sustainable use and the like; the application of the Antarctic krill oil after arsenic removal can be expanded, and the safety of the Antarctic krill oil is enhanced.)

1. A method for removing arsenic in Antarctic krill oil is characterized by comprising the following steps: and (3) dispersing the antarctic krill oil in an organic solvent, adding EDTA (ethylene diamine tetraacetic acid) grafted magnetic chitosan, and removing the EDTA grafted magnetic chitosan after ultrasonic oscillation reaction to obtain the antarctic krill oil with arsenic removed.

2. The method for removing arsenic from Antarctic krill oil according to claim 1, wherein the preparation method of EDTA grafted magnetic chitosan comprises: suspending EDTA dianhydride in methanol, adding an aqueous solution of magnetic chitosan, stirring at room temperature for about 12-24 h, ultrafiltering, mixing the precipitate with ethanol, and stirring for 6-12 h to obtain EDTA grafted magnetic chitosan.

3. The method for removing arsenic from Antarctic krill oil according to claim 2, wherein the mass ratio of EDTA dianhydride to magnetic chitosan is (3-5): 1.

4. the method for removing arsenic from Antarctic krill oil according to claim 2, wherein the method for preparing magnetic chitosan comprises: dispersing chitosan in acetic acid solution, introducing nitrogen, heating and stirring, adding Fe³⁺And Fe²⁺And (3) adjusting the pH value of the mixed salt solution to 8-9, stirring uniformly under the protection of inert gas, separating the magnetic chitosan by using an external magnetic field, alternately washing with deionized water and ethanol, and freeze-drying to obtain the magnetic chitosan.

5. The method for removing arsenic from Antarctic krill oil according to claim 4, wherein said iron-containing component³⁺And Fe²⁺Fe in the mixed salt solution of³⁺And Fe²⁺The mass ratio of (2-4): 1.

6. the method for removing arsenic from Antarctic krill oil according to claim 4, wherein the heating temperature is 65-80 ℃ and the stirring time is 15-35 min.

7. The method for removing arsenic from Antarctic krill oil according to claim 1, wherein the organic solvent is prepared from ethanol and water according to a volume ratio of (1-3): 1.

8. The method for removing arsenic from Antarctic krill oil according to claim 1, wherein the ultrasonic power is controlled to 120-150W and the ultrasonic frequency is controlled to 35-45 kHz in the ultrasonic oscillation reaction.

9. The method for removing arsenic from Antarctic krill oil according to claim 1, wherein the EDTA grafted magnetic chitosan is removed by an external magnetic field.

10. The method for removing arsenic from Antarctic krill oil according to claim 1, wherein 10-30 mg EDTA grafted magnetic chitosan is added to each ml of Antarctic krill oil.

Technical Field

The invention relates to the technical field of aquatic product processing, in particular to a method for removing arsenic in euphausia superba oil.

Background

At present, Antarctic krill has become the most important fishery resource in the world ocean fishing industry. The total fat content in the antarctic krill is rich, and the antarctic krill oil extracted from the antarctic krill contains rich Omega-3 (Omega-3) polyunsaturated fatty acid phospholipid and bioactive lipid such as astaxanthin. Research shows that the euphausia superba oil has multiple functions of resisting oxidation, resisting aging, eliminating free radicals, reducing blood fat, strengthening brain, benefiting intelligence and the like, and is applied to multiple fields of food, health-care products and the like. While euphausia superba is generally regarded as an important biological resource, the food safety of related products, particularly the content of toxic heavy metal arsenic contained in the euphausia superba, is concerned.

The antarctic krill oil has high total arsenic content, which causes people to have a certain doubt on the edible safety, so that an efficient and environment-friendly method for removing the arsenic in the antarctic krill oil is needed to be found. Besides glycerolipid, antarctic krill oil also contains a large amount of polar lipids such as phospholipid, and an emulsification phenomenon can be generated in the extraction process by adopting polar solvents such as methanol/water, so that the extraction efficiency and the detection accuracy are seriously influenced.

At present, methods for dearsenifying treatment of aquatic products mainly comprise resin adsorption, hydrogen peroxide removal and the like. The resin adsorption effect is general, and the regeneration of the resin is involved, so that the process is complex; the conditions for removing the hydrogen peroxide are harsh, so that the quality of the aquatic products is easy to change; the preservation of aquatic products, especially shrimps, mainly adopts sulfite as an inhibitor or an additive for delaying the blackening of the shrimps, but the method has potential safety hazard.

Chinese patent literature discloses a dearsenification and fresh-keeping treatment method for antarctic krill, the application publication number of which is CN 108935631A, the dearsenification and fresh-keeping of the antarctic krill are simultaneously carried out, the dearsenification and fresh-keeping effects are achieved by placing the antarctic krill in a water dispersion system of modified calcined shell powder and applying a pulse electric field, and the dearsenification rate can reach 40% -50%. However, the adsorbent used in the dearsenification process of the invention is not easy to filter and is easy to remain, which affects the purity of the antarctic krill product.

Disclosure of Invention

The invention provides an environment-friendly and easily-separated method for removing arsenic from euphausia superba oil, aiming at solving the problems that the traditional method for removing arsenic from euphausia superba oil is complex and an adsorbent is not easy to remove.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for removing arsenic in Antarctic krill oil comprises the following steps: and (3) dispersing the antarctic krill oil in an organic solvent, adding EDTA (ethylene diamine tetraacetic acid) grafted magnetic chitosan, and removing the EDTA grafted magnetic chitosan after ultrasonic oscillation reaction to obtain the antarctic krill oil with arsenic removed.

Ethylene Diamine Tetraacetic Acid (EDTA) is a metal chelating agent, has excellent metal adsorption capacity in a solution with a low pH value, has the effect of enhancing heavy metal adsorption, and is wrapped in the chelating agent through a strong binding effect, so that heavy metals in a target object are removed. EDTA is grafted to the magnetic chitosan, so that the easily-separated, efficient and environment-friendly green adsorbent can be obtained for removing arsenic in the antarctic krill oil.

Preferably, the preparation method of the EDTA grafted magnetic chitosan comprises the following steps: suspending EDTA dianhydride in methanol, adding a magnetic chitosan solution, stirring at room temperature for about 12-24 h, ultrafiltering, mixing the precipitate with ethanol, and stirring for 6-12 h to obtain EDTA grafted magnetic chitosan.

Preferably, the mass ratio of the EDTA dianhydride to the magnetic chitosan is (3-5): 1.

preferably, the preparation method of the magnetic chitosan comprises the following steps: dispersing chitosan in acetic acid solution (2%, v/v), introducing nitrogen, heating under stirring, and adding Fe³⁺And Fe²⁺And (3) adjusting the pH of the mixed salt solution to 8-9 (preferably adjusting with ammonia water), stirring uniformly under the protection of inert gas, separating the magnetic chitosan by using an external magnetic field, alternately washing with deionized water and ethanol, and freeze-drying to obtain the magnetic chitosan. The purpose of adjusting the pH value to 8-9 is to prevent Fe in the synthesis process²⁺Is oxidized.

Preferably, the heating temperature is 65-80 ℃, and the stirring time is 15-35 min.

Preferably, the Fe-containing compound³⁺And Fe²⁺Fe in the mixed salt solution of³⁺And Fe²⁺The mass ratio of (2-4): 1. controlling Fe in mixed salt solution³⁺And Fe²⁺In an amount to introduce Fe into chitosan₃O₄。

Magnetic shell polymerThe sugar is an economic, environment-friendly, recyclable and easily-separated high-efficiency adsorbent, and the Fe is₃O₄The introduction of the metal chelating agent EDTA can well improve the characteristic of poor stability of the chitosan in an acid solution, and the metal chelating agent EDTA is grafted to the surface of the magnetic chitosan, so that the heavy metal adsorption capacity of the magnetic chitosan can be effectively improved.

Preferably, the organic solvent is prepared from ethanol and water according to the volume ratio of (1-3): 1.

Preferably, in the ultrasonic oscillation reaction, the ultrasonic power is controlled to be 120-150W, and the ultrasonic frequency is controlled to be 35-45 kHz. The effect of the ultrasonic wave is not only dependent on the intensity and frequency of the ultrasonic wave, but also has a certain relation with the structural function of the crushed object, and the frequency of the ultrasonic wave should have a certain range of change because the size of the bubbles in the extraction medium is not single, but has a distribution range, namely a bandwidth.

Preferably, an external magnetic field is used for removing the EDTA grafted magnetic chitosan.

Preferably, 10-30 mg of EDTA grafted magnetic chitosan is added into each ml of antarctic krill oil.

Therefore, the invention has the following beneficial effects: the EDTA grafted magnetic chitosan microspheres are used for efficiently adsorbing and removing arsenic in the antarctic krill oil, and the material has the advantages of environmental friendliness, easiness in separation, sustainable use and the like; the application of the Antarctic krill oil after arsenic removal can be expanded, and the safety of the Antarctic krill oil is enhanced.

Detailed Description

The technical solution of the present invention is further specifically described below by way of specific examples.

In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.