CN100525640C - Rare-earth forage additive preparation method and use thereof - Google Patents
Rare-earth forage additive preparation method and use thereof Download PDFInfo
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- CN100525640C CN100525640C CNB200610053167XA CN200610053167A CN100525640C CN 100525640 C CN100525640 C CN 100525640C CN B200610053167X A CNB200610053167X A CN B200610053167XA CN 200610053167 A CN200610053167 A CN 200610053167A CN 100525640 C CN100525640 C CN 100525640C
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- earth
- rare earth
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Abstract
A RE-type forage additive is a cationic exchange resin containing active RE. It is prepared through adsorption and ion exchange between RE salt cationic exchange resin, filtering, drying and pulverizing. It can be added to forage proportionally (50-500 mg/kg).
Description
Technical field
The present invention relates to a kind of rare-earth forage additive and preparation and using method.
Background technology
Rare earth element comprises 15 kinds of elements (atomic number from 57 to 71) and the scandium in the lanthanide series, and totally 17 kinds of elements such as yttrium etc.According to they qualitative some differences, be divided into LREE (scandium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium) and heavy rare earth element (gadolinium, terbium, dysprosium, holmium, erbium, yttrium, thulium, ytterbium, lutetium).Wherein cerium accounts for 48%, and lanthanum accounts for 25%, and neodymium accounts for 16%, and samarium accounts for 2%, and praseodymium accounts for 5%, and other 12 kinds of elements only account for 4%.There is abundant rare earth resources in China, and commercial reserves reaches more than 3,600 ten thousand tons, accounts for 80% of world's gross reserves.
China also is that first rare earth is used for farming as commodity, and woods is herded, the country of agricultural productions such as fishing, so the research and development rare earth resources is the focus of basic research such as industrial or agricultural always.In recent years, in animal husbandry, widely applied studies show that the effect that rare earth has remarkable promotion growth of animals or poultry, improves efficiency of feed utilization and increase economic efficiency.Therefore the application of rare earth in animal husbandry become a popular research field, caused many scholars' concern.The rare-earth forage additive that uses comprises inorganic rare earth and organic RE, and the inorganic rare earth major product has nitric acid rare earth, sulfuric acid rare earth, carbonated rare earth, rare earth chloride; The organic RE major product has vitamin C rare earth, citric acid rare earth, amino-acid rare earth and chitin rare earth etc.
The rare earth adsorptivity is strong, very easily is adsorbed on the feed surface when mixing with feed, is difficult for mixing with feed.Should be earlier before batching with rare earth and the quantitative abundant mixing of talcum powder, make rare earth be rolled into fine particle, and then send into mixer and mix with feed by talcum powder, also available spraying water-solublely sprays in the feed rare earth is first again.Mostly present feeding experiment is industry or agriculture rare-earth products if adopting, the animal husbandry special use seldom, the composition difference is very big between various additives, thereby the suitable addition in being difficult to determine to produce.Rare earth element shows the best characteristics of the fastest stage effect of growth to the effect of growth of animals or poultry performance, and its consumption is strict, and every kind of livestock and poultry all have the best dosage of feeding, and are below or above optimal dose, not only somatotrophic advantage can not be shown, but also harmful effect might be produced.Therefore, add rare earth and will determine suitable dose according to livestock and poultry species, sex, age, raising condition, daily ration level and rare-earth products quality.
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, closing property of huge legendary turtle 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 cationic ion-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 cationic ion-exchange resin; Have alkaline functional base (strong basicity: quaternary ammonium group-N (CH
3)
3Deng; Alkalescent: 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 in 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 skeleton structure, and the 3rd bit digital is a serial number, in order to difference group, crosslinking agent etc.All macroreticular ion exchange resins add before model, and a 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 purifying 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 protection blood purification in the recent period.Since proposing ion exchange resin in 1956 first and being used to delay medicine as pharmaceutical carrier and discharging, utilizing ion exchange technique to delay the report that medicine discharges constantly increases, and has entered the practicality stage.Ion exchange resin has multiple good characteristic as pharmaceutical carrier, at present its controlled release, cutaneous penetration, site-specific delivery of drugs, instant, ion import 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.Mainly control medicine release in intestines and stomach of ion exchange resin, be ion exchange resin controlled-release administrating system (Ion-Exchange ResinControlled Drag Delivery System, IERCDDS), compare with other delivery 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 intestines and stomach, 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 rare-earth forage additive and preparation and using method.
Rare-earth forage additive is a kind of cationic ion-exchange resin that contains active rare earth that adopts trivalent rare earth salt and cationic ion-exchange resin to be prepared from through absorption, ion-exchange reactions, by weight percentage, the content of rare earth in cationic ion-exchange resin is 0.5～5%.
The preparation method of rare-earth forage additive may further comprise the steps:
1) cationic ion-exchange resin is placed 0.5～5mol/L hydrochloric acid solution of 1～4 times of resin volume soaked 3～6 hours, drain after the acid solution with water rinse to neutral;
2) will contain the trivalent rare earth salt that rare earth content is a cationic ion-exchange resin weight 0.5～5%, 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 3.5～6.5, room temperature reaction 5～10 hours;
3) detection step 2) the pH value of reactant liquor is regulated with alkaline solution, and making reacting liquid pH value is 7.0～8.5; Wash 3～6 times, filter or centrifugal dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.
The said rare earth of the present invention is to comprise in lanthanum, cerium, praseodymium, neodymium, samarium, promethium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, the scandium one or more.Rare-earth salts is single rare earth chloride or nitric acid rare earth, can be two or more rare earth chloride or nitric acid rare earth.Also can be two or more the rare earth chloride or the mixture of nitric acid rare earth.Alkaline solution is that concentration is the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus of 0.5～10moL/L.
The using method of rare-earth forage additive: add in aquatic livestock, ox, sheep, the animal and fowl fodder in the dosage of rare earth by the 50～500mg/kg that accounts for the feed gross weight.
Advantage of the present invention is:
(1) utilize cationic ion-exchange resin can play the characteristics of exchange interaction with cation, in cationic ion-exchange resin, implementation method is easy with rare earth loaded, 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 rare earth of institute's load is had the control slow releasing function, thereby improved the absorption rate of rare earth greatly.
(3) rare-earth forage additive of the present invention is easy to mix with feed, forms even disperse system, and is easy to use.
(4) the prepared rare-earth forage additive of the present invention various animals such as livestock and poultry, ox, sheep, rabbit, fish, shrimp that can be used for feeding have the growth of animal of promotion, improve resistance against diseases and survival rate, raising food utilization efficiency, improve function such as animal product quality.
The specific embodiment
Cationic ion-exchange resin comprises storng-acid cation exchange resin and weak-acid cation-exchange resin.Cationic ion-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, cationic ion-exchange resin can be gel-type or macroporous ion-exchange resin.The cationic ion-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 and the isopyknic 0.5mol/L hydrochloric acid solution of resin soaked 6 hours, drain after the acid solution with water rinse to neutral;
2) will contain the lanthanum chloride that the lanthanum amount is a cationic ion-exchange resin weight 0.5%, and 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 3.5, room temperature reaction 5 hours;
3) detection step 2) the pH value of reactant liquor is the sodium hydrate aqueous solution adjusting of 10moL/L with concentration, and making reacting liquid pH value is 7.0; Wash filtering means dehydration 3 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.By weight percentage, the content of rare earth in cationic ion-exchange resin is 0.5%.
Embodiment 2
1) with commercially available D001 macropore strong acid polystyrene cation conversion resin (this product is equivalent to the U.S.:
Amberlite200, West Germany: Lewaitet-SP120), place the 5mol/L hydrochloric acid solution of 4 times of resin volumes to soak 3 hours, drain after the acid solution with water rinse to neutral;
2) be that the terbium nitrate and the yttrium content of cationic ion-exchange resin weight 1% is the yttrium chloride of cationic ion-exchange resin weight 1% with terbium content, be pre-configured to the aqueous solution of 2.0mol/L, slowly add in the resin of step 1) in stirring down, the pH value of detection and conditioned reaction liquid is 6.5, room temperature reaction 10 hours;
3) detection step 2) the pH value of reactant liquor is the potassium hydroxide aqueous solution adjusting of 0.5moL/L with concentration, and making reacting liquid pH value is 8.5; Wash centrifugal dehydration 6 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.By weight percentage, the content of rare earth (terbium and yttrium) in cationic ion-exchange resin is 2.0%.
Embodiment 3
1) (this product is equivalent to the U.S.: Amberlite IR-132 with 001 * 12/14/16 commercially available strongly acidic styrene type cation exchange resin, IR-130, IR-124), place the 3mol/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;
2) be that the lanthanum chloride of cationic ion-exchange resin weight 1%, the cerous nitrate that cerium content is cationic ion-exchange resin weight 1%, chlorination mistake and the neodymium content that praseodymium content is cationic ion-exchange resin weight 0.5% are the neodymium nitrate of cationic ion-exchange resin weight 0.5% with lanthanum content, be pre-configured to the aqueous solution of 1.0mol/L, slowly add in the resin of step 1) in stirring down, the pH value of detection and conditioned reaction liquid is 5.0, room temperature reaction 8 hours;
3) detection step 2) the pH value of reactant liquor is the aqueous sodium carbonate adjusting of 1moL/L with concentration, and making reacting liquid pH value is 8.0; Wash filtering means dehydration 4 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.By weight percentage, the content of rare earth (lanthanum, cerium, praseodymium, neodymium) in cationic ion-exchange resin is 3%.
Embodiment 4
1) commercially available this product of D113 macropore acidulous acrylic acid cation exchanger resin is equivalent to Germany: LewatitCNP-80, the U.S.: AmberliteIRC-84), place the 1.5mol/L hydrochloric acid solution of 3 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral;
2) be that the lanthanum chloride of cationic ion-exchange resin weight 1%, the cerous nitrate that cerium content is cationic ion-exchange resin weight 1.5%, the praseodymium nitrate that praseodymium content is cationic ion-exchange resin weight 1%, erbium nitrate and the gadolinium concentrations that erbium content is cationic ion-exchange resin weight 1% are the gadolinium nitrate of cationic ion-exchange resin weight 0.5% with lanthanum content, be pre-configured to the aqueous solution of 0.5mol/L, slowly add in the resin of step 1) in stirring down, the pH value of detection and conditioned reaction liquid is 6.0, room temperature reaction 8 hours;
3) detection step 2) the pH value of reactant liquor is the sodium bicarbonate aqueous solution adjusting of 5moL/L with concentration, and making reacting liquid pH value is 8.0; Wash filtering means dehydration 4 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.By weight percentage, the content of rare earth (lanthanum, cerium, praseodymium, erbium, gadolinium) in cationic ion-exchange resin is 5%.
Claims (6)
1. rare-earth forage additive, it is characterized in that, it is a kind of cationic ion-exchange resin that contains active rare earth that adopts trivalent rare earth salt and cationic ion-exchange resin to be prepared from through absorption, ion-exchange reactions, by weight percentage, the content of rare earth in cationic ion-exchange resin is 0.5～5%, and the step of its preparation method is:
1) cationic ion-exchange resin is placed 0.5～5mol/L hydrochloric acid solution of 1～4 times of resin volume soaked 3～6 hours, drain after the acid solution with water rinse to neutral;
2) will contain the trivalent rare earth salt that rare earth content is a cationic ion-exchange resin weight 0.5～5%, 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 3.5～6.5, room temperature reaction 5～10 hours;
3) detection step 2) the pH value of reactant liquor is regulated with alkaline solution, and making reacting liquid pH value is 7.0～8.5; Wash 3～6 times, filter or centrifugal dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive;
Said rare earth is lanthanum, cerium, praseodymium, gadolinium, terbium, erbium, yttrium.
2. a kind of rare-earth forage additive according to claim 1 is characterized in that, said rare-earth salts is single rare earth chloride or nitric acid rare earth.
3. a kind of rare-earth forage additive according to claim 1 is characterized in that, said rare-earth salts is two or more the rare earth chloride or the mixture of nitric acid rare earth.
4. the preparation method of a rare-earth forage additive as claimed in claim 1 is characterized in that the step of method is as follows:
1) cationic ion-exchange resin is placed 0.5～5mol/L hydrochloric acid solution of 1～4 times of resin volume soaked 3～6 hours, drain after the acid solution with water rinse to neutral;
2) will contain the trivalent rare earth salt that rare earth content is a cationic ion-exchange resin weight 0.5～5%, 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 3.5～6.5, room temperature reaction 5～10 hours;
3) detection step 2) the pH value of reactant liquor is regulated with alkaline solution, and making reacting liquid pH value is 7.0～8.5; Wash 3～6 times, filter or centrifugal dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain rare-earth forage additive.
5. the preparation method of a kind of rare-earth forage additive according to claim 4 is characterized in that described alkaline solution is that concentration is the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus of 0.5～10mol/L.
6. an a kind of using method of rare-earth forage additive according to claim 1 is characterized in that adding in aquatic livestock, the animal and fowl fodder in the dosage of rare earth by the 50～500mg/kg that accounts for the feed gross weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610053167XA CN100525640C (en) | 2006-08-28 | 2006-08-28 | Rare-earth forage additive preparation method and use thereof |
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|---|---|---|---|
| CNB200610053167XA CN100525640C (en) | 2006-08-28 | 2006-08-28 | Rare-earth forage additive preparation method and use thereof |
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| CN1911071A CN1911071A (en) | 2007-02-14 |
| CN100525640C true CN100525640C (en) | 2009-08-12 |
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| CN106578477A (en) * | 2016-11-30 | 2017-04-26 | 周福弟 | Special feed for cattle and preparation method of special feed |
| CN108013253A (en) * | 2018-01-16 | 2018-05-11 | 常德九鼎农牧有限公司 | A kind of environment-friendly pig feed |
| CN110169497A (en) * | 2019-07-04 | 2019-08-27 | 湖南师范大学 | It is a kind of to adjust the feed addictive and its application that livestock and poultry enterocyte falls off |
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