阅读说明：本技术 一种低砷南极磷虾油及其制备方法 (Low-arsenic euphausia superba oil and preparation method thereof ) 是由 宗俊 范宁宁 甄方卉 于 2019-06-25 设计创作，主要内容包括：本申请公开了一种低砷南极磷虾油及其制备方法。所述方法包括如下步骤：S1、将初始南极磷虾油溶解于无水乙醇中,获得第一混合液；S2、将所述第一混合液与吸附剂混合进行脱砷处理,去除所述吸附剂后获得第二混合液；所述吸附剂由凹凸棒土负载FeCl<Sub>3</Sub>制成；S3、对所述第二混合液进行脱溶剂处理,获得所述低砷南极磷虾油。本发明所用吸附剂原料绿色环保、易制备,所用试剂安全无毒,操作设备简单易于实现,不仅降低了南极磷虾油中总砷的含量(总砷含量≤1mg/kg,磷脂含量≥30％),还保证了产品的安全性,扩大了南极磷虾油的适用范围。(The application discloses low-arsenic antarctic krill oil and a preparation method thereof. The method comprises the following steps: s1, dissolving the initial antarctic krill oil in absolute ethyl alcohol to obtain a first mixed solution; s2, mixing the first mixed solution with an adsorbent for dearsenification treatment, and removing the adsorbent to obtain a second mixed solution; the adsorbent is prepared by loading FeCl on attapulgite 3 Preparing; and S3, performing desolventizing treatment on the second mixed solution to obtain the low-arsenic antarctic krill oil. The adsorbent used in the invention has the advantages of green and environment-friendly raw materials, easy preparation, safe and nontoxic used reagents, simple and easy realization of operation equipment, reduction of the total arsenic content in the euphausia superba oil (the total arsenic content is less than or equal to 1mg/kg, and the phospholipid content is more than or equal to 30%), guarantee of the product safety, and expansion of the application range of the euphausia superba oil.)

1. A preparation method of low-arsenic antarctic krill oil comprises the following steps:

s1, dissolving the initial antarctic krill oil in absolute ethyl alcohol to obtain a first mixed solution;

s2, mixing the first mixed solution with an adsorbent for dearsenification treatment, and removing the adsorbent to obtain a second mixed solution; the adsorbent is prepared by loading FeCl on attapulgite₃Preparing;

and S3, performing desolventizing treatment on the second mixed solution to obtain the low-arsenic antarctic krill oil.

2. The method of claim 1, wherein: in step S2, the suction is performedFeCl in the additive₃The loading rate is 0.5% to 4%, preferably 1% to 3%, more preferably 2%.

3. The method of claim 1 or 2, wherein: in step S2, the first mixed liquor is mixed with the adsorbent according to 1/3-5 g of the adsorbent per gram of the initial antarctic krill mixed oil;

preferably, the first mixed liquor is mixed with the adsorbent according to the mixing of 2.5 to 4 grams of the adsorbent per gram of the initial antarctic krill oil;

more preferably, the first mixture is mixed with the adsorbent in a manner of mixing 3 grams of the adsorbent per gram of the initial antarctic krill oil.

4. A method as claimed in any one of claims 1 to 3, characterized by: in step S2, the temperature of the dearsenifying treatment is 20-62 ℃, preferably 30-60 ℃, and more preferably 60 ℃;

and/or the time of the dearsenification treatment is 30-60min, preferably 60 min.

5. The method of any of claims 1-4, wherein: in step S1, the mass ratio of the initial antarctic krill oil to the absolute ethanol used for the dissolution is 1 (3-15), preferably 1 (5-12), and more preferably 1: 10; the temperature of the dissolution is 20-65 ℃, preferably 50-65 ℃, and more preferably 60 ℃;

in step S3, the desolventizing mode is reduced pressure distillation, the temperature of the reduced pressure distillation is 50-62 ℃, preferably 60 ℃, and the vacuum degree of the reduced pressure distillation is less than or equal to-0.09 MPa.

6. The method of any of claims 1-5, wherein: in step S2, the adsorbent is prepared according to a method comprising the steps of:

s21, mixing the attapulgite with an acid solution to obtain activated attapulgite; the acid solution is hydrochloric acid solution, nitric acid solution or sulfuric acid solution, and preferably hydrochloric acid solution;

S22FeCl is added₃And fully mixing the solution with the activated attapulgite to obtain the adsorbent.

7. The method of claim 6, wherein: step S21, mixing attapulgite, a 1:2 hydrochloric acid solution and water according to the proportion of 4-6g, 1ml, 10-20ml, boiling for 30-40min, cooling, washing with water until the pH value is 4.5-5.5, heating to 400-450 ℃ for activation for 3-5h, crushing, and sieving with a sieve of 150-300 meshes to obtain activated attapulgite;

step S22 is to mix 0.005-0.02mol/L FeCl preferably 0.01mol/L₃And fully mixing the solution with the activated attapulgite, drying at the temperature of 100-120 ℃ for 15-30h, and sieving with a sieve of 150-300 meshes to obtain the adsorbent.

8. The method of any of claims 1-7, wherein: the total arsenic content in the low-arsenic antarctic krill oil is less than or equal to 1mg/kg, and the total phospholipid content is more than or equal to 30%.

9. A low-arsenic antarctic krill oil, produced by the method of any one of claims 1 to 8; the dosage form of the low-arsenic antarctic krill oil is capsule, microcapsule, tablet, powder or aqueous emulsion.

10. Use of the krill oil from Euphausia superba with low arsenic content according to claim 9 for the preparation of general foods, health foods, dietary supplements, and foods for special medicine.

Technical Field

The invention relates to the technical field of food, in particular to low-arsenic antarctic krill oil and a preparation method thereof.

Background

Antarctic krill belongs to Crustacea and Euphausiacea, and is widely distributed in Antarctic sea areas, and its name is because it emits strong phosphorescence at night and when frightened. Antarctic krill is small in size, is eaten by fine diatoms, has a storage amount of about 4-6 million tons, contains nutritional ingredients including proteins, lipids, minerals, active ingredients and the like, and is an open sea resource with high development and utilization values.

The antarctic krill oil is extracted from antarctic krill, is rich in phospholipid type omega-3 polyunsaturated fatty acid eicosapentaenoic acid (EPA), docosahexenoic acid (DHA), astaxanthin and other functional factors, can prevent cardiovascular and cerebrovascular diseases and inflammatory reaction, improves immunity, oxidation resistance and the like, and plays an important role in maintaining human health.

In recent years, due to the discharge of a large amount of industrial wastewater, arsenide is easy to enter aquatic organism tissues, so that the arsenide is enriched, and the total arsenic in aquatic products is relatively higher than that in other foods. The total arsenic content of antarctic krill oil is about 4-7ppm, most of which is organic arsenic, but the application of the antarctic krill oil in health food is limited. In order to expand the applicability of the antarctic krill oil, ensure the quality safety of products and reduce the total arsenic content of the antarctic krill oil, the demand is high.

At present, the patents related to dearsenization of Antarctic krill oil and the disadvantages thereof are as follows:

201710296022.0 patent uses ethanol water solution to wash raw materials, uses ethyl acetate and ethanol to extract according to mixed solvent of any proportion, adds absorbent (active carbon, diatomite, attapulgite or chitosan) into extract, and removes solvent by reduced pressure distillation, to obtain the low-arsenic antarctic krill oil composition with total arsenic content of 0.5-2 ppm. The patent uses mixed solvent for extraction, is not beneficial to the recycling of the solvent, has certain toxicity to the ethyl acetate to influence the safety of the product, takes the extracting solution as an adsorption object and is not beneficial to operation.

Patent 201710813399.9 discloses adding sodium alginate magnetic microsphere adsorbent into antarctic krill oil, stirring for 6-8min with the adsorbent concentration in the mixed solution being 3.1-3.7g/L, and performing magnetic separation to obtain the antarctic krill oil after adsorption. The patent relates to the use of metal ions, has food safety hidden danger, and the step of making the adsorbent is comparatively loaded down with trivial details in addition, relates to the use of a large amount of reagents, equipment, has increased manufacturing cost, and does not mark the minimum arsenic content of dearsenic antarctic krill oil that finally obtains.

Patent 201710720339.2 uses 96-99% ethanol water solution to extract antarctic krill powder for 0.5-2.5h, standing and precipitating to obtain supernatant, filtering with ceramic membrane (aperture 0.1-5um, operating pressure 0.4-0.6MPa) to obtain filtrate, washing the filtrate with alkaline solution, stirring, standing, collecting oil phase liquid, and removing arsenic with chromatographic column (silica gel column, alumina column, polyamide column, cation exchange resin). After the antarctic krill powder is extracted, the content of arsenic is reduced by ceramic membrane filtration and cation exchange resin adsorption, certain requirements are provided for production equipment of enterprises, the production cost is increased, and the oil yield of the dearsenic antarctic krill oil is not indicated.

Patent 201810267685.4 pre-heats Antarctic krill at 60 deg.C for 1min after cutting or grinding into powder, contacts with steam injector under pressure of at least 100kpa for 1-5min, cuts or grinds to obtain viscous phospholipid after temperature reaches 100-. And extruding the partially defatted solid to obtain a pressed liquid of residual solid particles and the partially defatted solid, adding water into the pressed liquid, adjusting the pH of the mixture to 4-6 by using HCl, and performing acid washing to separate a water phase and an oil phase to obtain the low-arsenic fluorine-free krill oil. According to the patent, the production process of fresh antarctic krill is utilized to reduce the content of arsenic in the antarctic krill oil, raw materials are not easy to transport and store, and the production cost of enterprises is improved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the low-arsenic antarctic krill oil and the preparation method thereof₃Loaded on the surface of the attapulgite to prepare the attapulgite loaded FeCl₃The adsorbent is prepared by dissolving Euphausia superba oil produced by oneself with polyploid food grade absolute ethyl alcohol, and adding attapulgite loaded FeCl₃The adsorbent is used for dearsenifying, and the self-produced euphausia superba oil is easy to obtain and convenient to store; the dearsenification step is simple and easy to operate, safe and nontoxic, the material of the adsorbent is green and environment-friendly, low in price and easy to obtain, the operation equipment is simple, the enterprise cost is saved, and the preparation is easy.

In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:

a preparation method of low-arsenic antarctic krill oil comprises the following steps:

s1, dissolving the initial antarctic krill oil in absolute ethyl alcohol to obtain a first mixed solution; the absolute ethyl alcohol is safe and non-toxic, and avoids the residue of toxic and harmful substances in the shrimp sauce;

s2, adsorbing the first mixed solutionMixing the agents, performing dearsenification treatment, and removing the adsorbent to obtain a second mixed solution; the adsorbent is prepared by loading FeCl on attapulgite₃Preparing;

and S3, performing desolventizing treatment on the second mixed solution to obtain the low-arsenic antarctic krill oil.

In the above method, in step S2, the FeCl in the adsorbent₃Loading Rate (FeCl loaded by Attapulgite in unit weight)₃Amount) of 0.5% to 4%, preferably 1% to 3%, more preferably 2%;

in the above method, in step S2, the first mixed liquor is mixed with the adsorbent according to 1/3-5 grams of the adsorbent per gram of the initial antarctic krill oil;

preferably, the first mixed liquor is mixed with the adsorbent according to the mixing of 2.5 to 4 grams of the adsorbent per gram of the initial antarctic krill oil;

more preferably, the first mixture is mixed with the adsorbent in a manner of mixing 3 grams of the adsorbent per gram of the initial antarctic krill oil.

In the above method, in step S2, the temperature of the dearsenification treatment is 20 to 62 ℃, preferably 30 to 60 ℃, and more preferably 60 ℃;

and/or the time of the dearsenification treatment is 30-60min, preferably 60 min.

In the above method, in step S1, the mass ratio of the initial antarctic krill oil to the absolute ethanol used for the dissolution is 1 (3-15), preferably 1 (5-12), more preferably 1: 10; the smaller the mass ratio of the shrimp sauce to the absolute ethyl alcohol is, the smaller the loss of the shrimp sauce in the adsorption process is, and the comprehensive consideration on the selection of the production cost is more suitable to be 1: 10;

the temperature of the dissolution is 20-65 ℃, preferably 50-65 ℃, more preferably 60 ℃.

In the above method, in step S2, the adsorbent is prepared according to a method comprising the steps of: s21, mixing the attapulgite with a hydrochloric acid solution to obtain activated attapulgite; the acid solution is hydrochloric acid solution, nitric acid solution or sulfuric acid solution, and preferably hydrochloric acid solution;

s22, mixing the powder with 0.005-0.02mol/L FeCl, preferably 0.01mol/L₃And fully mixing the solution with the activated attapulgite to obtain the adsorbent.

In the method, step S21 is mixing attapulgite, 1:2 hydrochloric acid solution and water according to the proportion of 4-6g:1ml:10-20ml, boiling for 30-40min, cooling, washing with water until the PH is 4.5-5.5, heating to 400-;

step S22 is FeCl₃Fully mixing the solution with the activated attapulgite, drying at the temperature of 100-120 ℃ for 15-30h, and sieving with a sieve of 150-300 meshes to obtain the adsorbent;

in the above method, in step S3, the desolventizing is carried out by distillation under reduced pressure,

the temperature of the reduced pressure distillation is 50-62 ℃, preferably 60 ℃,

the vacuum degree of the reduced pressure distillation is less than or equal to-0.09 MPa.

In the method, the total arsenic content in the low-arsenic Antarctic krill oil is less than or equal to 1mg/kg, and the total phospholipid content is more than or equal to 30%.

In the above method, in step S2, the method for removing the adsorbent is filtration.

The invention also provides the low-arsenic antarctic krill oil which is prepared by any one of the methods, and the dosage form of the low-arsenic antarctic krill oil is capsule, microcapsule, tablet, powder or aqueous emulsion.

The invention protects the application of the low-arsenic antarctic krill oil in preparing common food, health food, dietary supplement and special medical food.

The invention has the following beneficial effects:

according to the invention, attapulgite with a large specific surface area and no harsh requirements on adsorption conditions is combined with ferric iron to form arsenic coordination complex, and the used adsorbent is green and environment-friendly in raw material, low in price, easy to operate and high in adsorption rate; the used equipment is simple and easy to realize; the used reagent is safe and nontoxic, and the product safety is high. Different adsorption conditions are adjusted to prepare the antarctic krill oil with different indexes, and the indexes of the obtained dearsenized antarctic krill oil can meet the conditions that the total arsenic content is less than or equal to 1mg/kg and the total phospholipid content is more than or equal to 30 percent.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The preparation method of the low-arsenic antarctic krill oil in the following examples comprises the following steps:

1. attapulgite activation

Taking attapulgite with a certain mass, adding a hydrochloric acid solution (1:2) and deionized water (the mass of the attapulgite: the volume of the hydrochloric acid solution: the volume of the deionized water is 5g:1ml:15ml) with a certain volume, boiling for 35min, cooling, washing with the deionized water until the pH is approximately equal to 5, heating to 420 ℃ to activate for 4h, crushing, and sieving with a 200-mesh sieve to obtain the activated attapulgite.

2. Attapulgite loaded FeCl₃Preparation of the adsorbent

Taking FeCl with a certain concentration (0.01mol/L)₃Slowly adding the activated attapulgite with a certain mass obtained in the step 1 into the solution, mechanically stirring and uniformly mixing, drying the mixture in an oven at 105 ℃ for 24 hours, taking out, cooling, crushing and sieving with a 200-mesh sieve to obtain the attapulgite-loaded FeCl₃An adsorbent.

3. Dearsenization of Antarctic krill oil

3.1, adding food-grade absolute ethyl alcohol (the mass ratio is 1:5-1:12) into the euphausia superba oil produced from the euphausia superba, fully dissolving at 30-60 ℃, and uniformly mixing to prepare the euphausia superba oil-ethanol mixed solution.

3.2, adding 1/3-5 times of attapulgite loaded FeCl of the shrimp sauce in the 3.1 Antarctic krill oil ethanol mixed solution₃And (3) adsorbing with an adsorbent, adjusting the temperature to 20-60 ℃, and mechanically stirring for 30-60min to perform dearsenization treatment.

And 3.3, filtering to remove the adsorbent in the treatment liquid of 3.2, distilling under reduced pressure and desolventizing at the temperature of 60 ℃ and the vacuum degree of less than or equal to-0.09 MPa to obtain the arsenic-removed euphausia superba oil.

4. Calculation of Antarctic krill oil yield after dearsenification

Wherein A is the yield of Antarctic krill oil after dearsenification, M₁The mass (g) of the Antarctic krill oil after arsenic removal, M₀The mass (g) of the original antarctic krill oil is shown.

5. Calculation of Total arsenic adsorption Rate

Wherein B is total arsenic adsorption rate, X₁The total arsenic (mg/kg) of the Antarctic krill oil after dearsenification is X₀The total arsenic (mg/kg) of the original Antarctic krill oil.

6. Euphausia superba oil index detection

The total arsenic content is determined by the second hydride generation atomic fluorescence spectrometry in GB5009.11-2014 determination of total arsenic and inorganic arsenic in food.

The total phospholipid content is determined by a molybdenum blue colorimetric method according to the first method in GB/T5537-2008 determination of phospholipid content in grain and oil inspection.