CN100415297C - Zinc supplements based on cation exchange resin and its preparation method and use - Google Patents

Zinc supplements based on cation exchange resin and its preparation method and use Download PDF

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Publication number
CN100415297C
CN100415297C CNB2006100531684A CN200610053168A CN100415297C CN 100415297 C CN100415297 C CN 100415297C CN B2006100531684 A CNB2006100531684 A CN B2006100531684A CN 200610053168 A CN200610053168 A CN 200610053168A CN 100415297 C CN100415297 C CN 100415297C
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zinc
exchange resin
cation exchange
resin
preparation
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CN1911448A (en
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胡彩虹
徐勇
夏枚生
姚志通
朱兴一
张红梅
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

A Zn supplement based on cationic exchange resin is a cationic exchange resin containing active Zn (1.5-10 Wt%), and can be used as the forage additive or for preparing health-care food or medicine to supplement Zn to human body. Its preparing process includes such steps as adsorptive ion exchange reaction between Zn salt and cationic exchange resin, filtering, drying and pulverizing.

Description

Preparation method based on the Zinc supplements of cation exchange resin
Technical field
The present invention relates to Zinc supplements and preparation method and purposes based on cation exchange resin.
Background technology
Zinc is the essential trace element of body, proved that now zinc participates in the animal body composition of kind of enzyme and functional protein surplus in the of 300, it not only participates in the metabolism of DNA, RNA, protein, saccharide, lipid and vitamin, mineral in animal body, and relevant with activity with the function of insulin, glucagon, prostaglandin, promoting sexual gland hormone etc.In addition, zinc still is the constituent of many functional proteins such as metallothionein, nucleoprotein, receptor etc., so zinc has biochemical functions widely.The zinc nutrition agent can be divided into: 1) inorganic zinc: comprise zinc sulfate, zinc oxide, zinc carbonate, zinc sulfide etc.Typical case in the inorganic zinc is represented as zinc sulfate, has only 7% according to " Chinese medicine voluminous dictionary " record absorption by human body rate, and can cause bad gastrointestinal reaction such as nauseating, vomiting.2) organic synthesis zinc: comprise zinc gluconate, zinc oxalate, zinc citrate, zinc lactate, zinc glycyrrhetate etc., it is compared with inorganic zinc, notable attribute is that the gastrointestinal stimulation is obviously reduced, and oral absorption utilization rate height, and the absorption by human body rate is 14%.3) amino-acid chelate type: under certain process conditions, formed through chelating by metallic elements such as aminoacid and zinc.4) biofermentation type: by selecting suitable barms, under specific condition of culture, in culture medium, add zinc, make in the yeast cells of results and be rich in zinc.In view of zinc is the nutrient that has important physiological function in the human body, the development of the efficient zinc extra-nutrition of low toxicity agent will be the direction of following trace element zinc nutrient research with exploitation.
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, carry chamber, 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 Zinc supplements and preparation method and purposes based on cation exchange resin.
Zinc supplements based on cation exchange resin is a kind of cation exchange resin that contains active zinc that adopts zinc salt and cation exchange resin to be prepared from through absorption, ion-exchange reactions, by weight percentage, the content of zinc in cation exchange resin is 1.5~10%.
Preparation method based on the Zinc supplements of cation exchange resin may further comprise the steps:
1) cation 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;
2) with zinc content be the zinc salt of cation exchange resin weight 1.5~10%, be pre-configured to the aqueous solution of 0.1~2.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 4.0~6.0, room temperature reaction 5~10 hours;
3) detection step 2) pH value of reactant liquor is regulated with alkaline solution, and making reacting liquid pH value is 6.5~8.0; Wash 3~5 times, filter or centrifuge dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain Zinc supplements based on cation exchange resin.
Zinc salt of the present invention is zinc chloride, zinc nitrate, zinc acetate or zinc sulfate.Alkaline solution of the present invention is that concentration is the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or the potassium bicarbonate of 0.5~5moL/L.
Zinc supplements based on cation exchange resin is used as poultry, aquatic animal, cattle, sheep zinc supplement feed additive.
Zinc supplements based on cation exchange resin is used as health product and the medicine for preparing human oral zinc reinforcing and treat human diseases by the zinc of drug treatment.
Advantage of the present invention is:
(1) utilize cation exchange resin can play the characteristics of exchange interaction with cation, zinc is loaded in the cation 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 zinc of institute's load is had the control slow releasing function, thereby improved the absorption rate of zinc greatly.
(3) the prepared Zinc supplements based on cation exchange resin of the present invention can be used as the zinc supplement that feed additive is applied to poultry, aquatic animal, cattle, sheep etc.; Also can be used for preparing human oral zinc reinforcing and treat the health product and the medicine of human diseases by the zinc of drug treatment, the scope of application is extensive.
(4) Zinc supplements based on cation exchange resin of the present invention is easy to mix with feedstuff, forms homodisperse system, and is easy to use.
The specific embodiment
Cation exchange resin comprises storng-acid cation exchange resin and weak-acid cation-exchange resin.Cation exchange resin comprises highly acid (sulfonic group ,-SO for having the acid function base 3H) and faintly acid (carboxylic acid group-COOH, phosphate-PO 3H 2) functional group, the polymer that can exchange with cation.According to the difference of resin physical arrangement, cation exchange resin can be gel-type or macroporous ion-exchange resin.The cation exchange resin skeleton is polystyrene or acrylic acid series.
Embodiment 1
1) (this product is equivalent to the U.S.: AmberrliteIR-120 Dowex-50 with 001 * 7 commercially available strongly acidic styrene type cation exchange resin, West Germany: Lewatit-100, Japan: DiaonSK-1), place with the isopyknic 0.5mol/L hydrochloric acid solution of resin and soaked 5 hours, drain after the acid solution with water rinse to neutral, add with the isopyknic water of resin again and make reactant liquor;
2) be the zinc chloride of cation exchange resin weight 1.5% with zinc content, be pre-configured to the aqueous solution of 0.1mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 4.0, room temperature reaction 5 hours;
3) the detection step 2) pH value of reactant liquor is the sodium hydrate aqueous solution adjusting of 0.5mol/L with concentration, and making reacting liquid pH value is 6.5; Wash filtering means dehydration 3 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain Zinc supplements based on cation exchange resin.By weight percentage, the content of zinc in cation exchange resin is 1.5%.
Embodiment 2
1) (this product is equivalent to the U.S.: Amberlite200 with commercially available D001 large hole strong acid styrene system cation exchange resin; Germany: Lewatit-SP210), place the 2mol/L hydrochloric acid solution of 2 times of resin volumes to soak 2 hours, drain after the acid solution with water rinse to neutral, the water that adds 2 times of resin volumes is again made reactant liquor;
2) be the zinc nitrate of cation exchange resin weight 10% with zinc content, be pre-configured to the aqueous solution of 2.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 6.0, room temperature reaction 10 hours;
3) the detection step 2) pH value of reactant liquor is the potassium hydroxide aqueous solution adjusting of 5moL/L with concentration, and making reacting liquid pH value is 8.0; Wash centrifuge dehydration 5 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain Zinc supplements based on cation exchange resin.By weight percentage, the content of zinc in cation exchange resin is 10%.
Embodiment 3
1) (this product is equivalent to Germany: LewatitCNP-80 with commercially available D113 macropore acidulous acrylic acid cation exchanger resin, the U.S.: AmberliteIRC-84), place the 1mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 3 hours, drain after the acid solution with water rinse to neutral, the water that adds 1.5 times of resin volumes is again made reactant liquor;
2) be the zinc sulfate of cation exchange resin weight 5.0% with zinc content, be pre-configured to the aqueous solution of 1.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 5.0, room temperature reaction 6 hours;
3) the detection step 2) pH value of reactant liquor is the aqueous sodium carbonate adjusting of 1moL/L with concentration, and making reacting liquid pH value is 7.5; Wash filtering means dehydration 4 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain Zinc supplements based on cation exchange resin.By weight percentage, the content of zinc in cation exchange resin is 5.0%.

Claims (3)

1. preparation method based on the Zinc supplements of cation exchange resin is characterized in that the step of method is as follows:
1) cation 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;
2) with zinc content be the zinc salt of cation exchange resin weight 1.5~10%, be pre-configured to the aqueous solution of 0.1~2.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 4.0~6.0, room temperature reaction 5~10 hours;
3) detection step 2) pH value of reactant liquor is regulated with alkaline solution, and making reacting liquid pH value is 6.5~8.0; Wash 3~5 times, filter or centrifuge dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain Zinc supplements based on cation exchange resin.
2. the preparation method of a kind of Zinc supplements based on cation exchange resin according to claim 1 is characterized in that described zinc salt is zinc chloride, zinc nitrate, zinc acetate or zinc sulfate.
3. the preparation method of a kind of Zinc supplements based on cation exchange resin according to claim 1 is characterized in that described alkaline solution is that concentration is the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or the potassium bicarbonate of 0.5~5moL/L.
CNB2006100531684A 2006-08-28 2006-08-28 Zinc supplements based on cation exchange resin and its preparation method and use Expired - Fee Related CN100415297C (en)

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US20220411285A1 (en) * 2019-11-28 2022-12-29 Bwt Holding Gmbh Cartridge for treating drinking water, and method for enriching drinking water with silicon
CN113333035A (en) * 2021-04-14 2021-09-03 浙江沁园水处理科技有限公司 Preparation method and application of strontium-type resin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947572A (en) * 1974-07-01 1976-03-30 Abbott Laboratories Iron-resin adsorbate
CN1063221A (en) * 1990-12-21 1992-08-05 理查森-维克斯有限公司 Polyamine drug-resin complexes
CN1546008A (en) * 2003-12-02 2004-11-17 沈阳药科大学 Ambroxol hydrochloride liquid sustained release preparation and preparation method thereof
CN1618427A (en) * 2003-11-21 2005-05-25 沈阳药科大学 Medicinal resin biological adhering slow-releasing liquid prepn. contg. aciclovir, and its prepn. method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947572A (en) * 1974-07-01 1976-03-30 Abbott Laboratories Iron-resin adsorbate
CN1063221A (en) * 1990-12-21 1992-08-05 理查森-维克斯有限公司 Polyamine drug-resin complexes
CN1618427A (en) * 2003-11-21 2005-05-25 沈阳药科大学 Medicinal resin biological adhering slow-releasing liquid prepn. contg. aciclovir, and its prepn. method
CN1546008A (en) * 2003-12-02 2004-11-17 沈阳药科大学 Ambroxol hydrochloride liquid sustained release preparation and preparation method thereof

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