A kind of preparation method of Selenium supplement agent
Technical field
The present invention relates to a kind of Selenium supplement agent and preparation method and purposes.
Background technology
Selenium is the essential trace element of animal body, has multiple important biological function, the Radical Metabolism of appreciable impact animal body, antioxidation, immunity, reproduction, apoptosis and endocrine hormone etc.The multiple disease of animal, all relevant as degradation under piglet white muscle disease, the Fructus Mori heart, chickling exudative diathesis and the livestock reproduction rate with selenic shortage.The daily ration selenium supplement is existing, and oneself is that China's aquaculture prevention lacks selenic conventional measure.On the other hand, along with deepening continuously that selenium is studied, its clinical practice also more and more is subjected to preclinical medicine and clinical medical attention.
Widely used selenium source is a sodium selenite in the livestock and poultry diet, but because sodium selenite has stronger toxicity and lower bioavailability, and have the Oxidation of helping, can cause harmful effect to animal and environment.Therefore some countries have limited the selemium nutrition supplement that use inorganic salt form, must use organic selenium as Sweden's regulation piglet feed, and Japan forbids adding sodium selenite class inorganic selenium in animal feed.Therefore, the exploitation low toxicity, selenium source is the emphasis of selemium nutrition research always efficiently.
Ion exchange resin (Ion exchange resin, IER) be the cancellated macromolecular compound that a class has functional group, its structure is made up of three parts: insoluble three dimensions mesh skeleton, be connected functional group on the skeleton and functional group with the exchangeable ion of opposite charges.According to the different in kind of cation exchange groups, ion exchange resin is divided into six big classes: storng-acid cation exchange resin, weak-acid cation-exchange resin, strong alkalinity anion literary composition change resin, weak-base anion-exchange resin, sequestration ion exchange resin, amphoteric ion-exchange resin, oxidation-reduction quality ion exchange resin.According to resin with tradable ionic nature, ion exchange resin is divided into cation exchange resin and anion exchange resin substantially, has acid function base (highly acid: sulfonic group (SO
3H); Faintly acid: carboxylic acid group (COOH), phosphate (PO
3H
2) etc.), the polymer that can exchange with cation is cation exchange resin; Have alkaline functional base (strong basicity: quaternary ammonium group-N (CH
3)
3Deng; Alkalescence: the primary, the second month in a season, tertiary amine groups (CH
2NH
2,--CH
2NHR ,-CH
2NR
2) etc.), the polymer that can exchange with anion is anion exchange resin.
According to the difference of resin physical arrangement, can be divided into gel-type and macroporous ion-exchange resin two big classes to ion exchange resin again.Gel type resin is the ion exchange resin of the homogeneous phase high-molecular gel structure of a class appearance transparent, the interior mutually micropore that produces of suction back resin, and counter ion can diffuse into and carry out ion exchange in the micropore that is produced by suction.The basic characteristics of macroreticular ion exchange resin be do in whole resin inside, wet or contraction, swelling all exist the duct more, bigger than general gel-type in water, thereby surface area is big, in ion exchange process, the easy diffusion mobility of ion, exchange velocity is very fast.
Full name of ion exchange resin claims to be rearranged by specific name, skeleton (or group) title, basic designation.The model name of ion exchange resin is different and fixed according to structure, form by three Arabic numerals: the classification of the first bit digital representative products, second-order digit is represented the difference of framing structure, and the 3rd bit digital is a serial number, in order to difference group, cross-linking agent etc.All macroreticular ion exchange resins add before model, and-D represents: gel-type ion-exchange resin connects Arabic numerals with " * " and represents after model.Wherein, classification designator has 0,1,2,3,4,5,6, corresponding representative strong-acid type, weak-type, strong base, weak base type, chelating type, both sexes and oxidation-reduction ion-exchange resin.The skeleton code name has 0,1, and 2,3 etc., represent polystyrene, acrylic acid series, phenolic aldehyde system, epoxy system etc. respectively.
Separation and purification pure water preparation that ion exchange resin is applied to analytical chemistry medicine for a long time reach fields such as being used for the environmental conservation blood purification in the recent period.Since proposing ion exchange resin first in 1956 and being used to delay drug release as pharmaceutical carrier, the report that utilizes ion exchange technique to delay drug release constantly increases, and has entered the practicality stage.Ion exchange resin has multiple good characteristic as pharmaceutical carrier, at present its controlled release, transdermal administration, site-specific delivery of drugs, instant, iontophoresis transdermal, nasal cavity, topical and cover side such as bitter taste of drug and application very deep research is all arranged, some product goes on the market.Ion exchange resin is control drug release in gastrointestinal tract mainly, be ion exchange resin controlled-release administrating system (Ion-Exchange ResinControlled Drag Delivery System, IERCDDS), compare with other drug-supplying systems, the main feature of IERCDDS is the volume that the release of medicine does not rely on pH value, enzymatic activity, temperature and gastrointestinal fluid in the gastrointestinal tract, because ionic species and strength maintenance thereof in the gastrointestinal fluid are constant relatively, so medicine can constant rate of speed discharge in vivo.
Summary of the invention
The purpose of this invention is to provide a kind of Selenium supplement agent and preparation method and purposes.
Selenium supplement agent is a kind of commutative selenate radical or ionic anion exchange resin of selenite radical of containing, and by weight percentage, the content of selenium in anion exchange resin is 0.1~1.0%.
The preparation method of Selenium supplement agent may further comprise the steps:
1) anion exchange resin is placed 0.5~2mol/L hydrochloric acid solution of 1~2 times of resin volume soaked 2~5 hours, drain after the acid solution with water rinse to neutral, 0.5~2mol/L sodium hydroxide solution with 1~2 times of resin volume soaked 3~6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) is packed in the exchange column, with selenium content is the selenium salt of anion exchange resin weight 0.1~1.0%, is configured to the selenium salt aqueous solution of 0.1~1mol/L, passes through exchange column with the flow velocity of 1~10mL/min, room temperature reaction 2~5 hours is washed 2~4 times;
3) with step 2) oven dry under being lower than 70 ℃ of the selenic anion exchange resin of gained load, obtain Selenium supplement agent.
The selenium salt that uses in the invention is Na
2SeO
3, K
2SeO
3, Na
2SeO
4Or K
2SeO
4
Selenium supplement agent is as cattle, sheep, poultry, aquatic animal selenium-supplementing feed additive.Health product and medicine that Selenium supplement agent is used to prepare human Orally taken selenium-replenishing and treats human diseases by the selenium of drug treatment.
Advantage of the present invention is:
(1) utilize anion exchange resin can play the characteristics of exchange interaction with anion, selenate radical or selenite radical are loaded in the anion exchange resin, implementation method is easy, suitability for industrialized production, and cost is lower.
(2) because ion exchange resin is a kind of control slow-released carrier of function admirable, the selenium of institute's load is had the control slow releasing function, thereby improved selenic absorption rate greatly.
(3) Selenium supplement agent of the present invention has low toxicity, characteristics of high efficiency, can be used as selenium-supplementing feed additive; The health product and the medicine that also can be used for preparing human Orally taken selenium-replenishing and treat human diseases by the selenium of drug treatment.
The specific embodiment
Anion exchange resin is strong-base anion-exchange resin or weak-base anion-exchange resin, has the alkaline functional base, comprises strong basicity (quaternary ammonium group-N (CH
3)
3) and alkalescence (primary, secondary, tertiary amine groups ,-CH
2NH
2,--CH
2NHR ,-CH
2NR
2) functional group.According to the difference of anion exchange resin physical arrangement, can be gel-type or macroporous ion-exchange resin.The anion exchange resin skeleton is polystyrene or acrylic acid series.
Embodiment 1
1) (this product is equivalent to the U.S.: AmberliteIRA-400 with 201 * 7 commercially available strong-basicity styrene series anion exchange resins, West Germany: LewatitM500, Japan: DiaionSA-10A), place the 0.5mol/L hydrochloric acid solution of 1 times of resin volume to soak 2 hours, drain after the acid solution with water rinse to neutral, 0.5mol/L sodium hydroxide solution with 1 times of resin volume soaked 3 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the Na of anion exchange resin weight 0.1% with selenium content
2SeO
3, be configured to the Na of 0.1mol/L
2SeO
3Aqueous solution, by exchange column, room temperature reaction 2 hours is washed 2 times with the flow velocity of 1mL/min;
3) with step 2) oven dry under being lower than 70 ℃ of the selenic anion exchange resin of gained load, obtain Selenium supplement agent.By weight percentage, the content of selenium in anion exchange resin is 0.1%.
Embodiment 2
1) (this product is equivalent to the U.S.: AmberliteIRA402 with commercially available 201 * semi-finals basicity styrene series anion exchange resin, Germany: Lewatit M504MB), place the 2mol/L hydrochloric acid solution of 2 times of resinites to soak 5 hours, drain after the acid solution with water rinse to neutral, 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the K of anion exchange resin weight 1.0% with selenium content
2SeO
3, be configured to the K of 1mol/L
2SeO
3Aqueous solution, by exchange column, room temperature reaction 5 hours is washed 4 times with the flow velocity of 10mL/min;
3) with step 2) oven dry under being lower than 70 ℃ of the selenic anion exchange resin of gained load, obtain Selenium supplement agent.By weight percentage, the content of selenium in anion exchange resin is 1.0%.
Embodiment 3
1) with commercially available D201 macroporous strong basic styrene series anion exchange resin (the suitable U.S. of this product: AmberliteIRA-900, West Germany: Lewatit MP-500, Japan: Diaion308), place the 1mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, 1mol/L sodium hydroxide solution with 1.5 times of resin volumes soaked 5 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the Na of anion exchange resin weight 0.8% with selenium content
2SeO
4, be configured to the Na of 0.5mol/L
2SeO
4Aqueous solution, by exchange column, room temperature reaction 3 hours is washed 3 times with the flow velocity of 5mL/min;
3) with step 2) oven dry under being lower than 70 ℃ of the selenic anion exchange resin of gained load, obtain Selenium supplement agent.By weight percentage, the content of selenium in anion exchange resin is 0.8%.
Embodiment 4
1) (this product is equivalent to the U.S.: AmberliteIRA-68 with commercially available D311 macroreticular weakly base acrylic acid type anion exchange resin; Germany: AP-49), place the 0.5mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, the 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 4 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the K of anion exchange resin weight 0.5% with selenium content
2SeO
4, be configured to the K of 0.8mol/L
2SeO
4Aqueous solution, by exchange column, room temperature reaction 2 hours is washed 2 times with the flow velocity of 2mL/min;
3) with step 2) oven dry under being lower than 70 ℃ of the selenic anion exchange resin of gained load, obtain Selenium supplement agent.By weight percentage, the content of selenium in anion exchange resin is 0.5%.
Selenium supplement agent of the present invention as the using method of the selenium-supplementing feed additive of poultry, aquatic animal, cattle, sheep is: admix in the feedstuff by 0.1~1.0 milligram of selenic dosage of per kilogram feedstuff.
Selenium supplement agent of the present invention is used to prepare human Orally taken selenium-replenishing and treats the health product of human diseases and the method for medicine is by the selenium of drug treatment: everyone every day, conventional selenium supplement amount was 50~100 micrograms, and treatment selenium supplement amount is 100~300 micrograms.