CN100569094C - A kind of cobalt-supplement forage additive and preparation and using method - Google Patents

A kind of cobalt-supplement forage additive and preparation and using method Download PDF

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Publication number
CN100569094C
CN100569094C CNB2006100531769A CN200610053176A CN100569094C CN 100569094 C CN100569094 C CN 100569094C CN B2006100531769 A CNB2006100531769 A CN B2006100531769A CN 200610053176 A CN200610053176 A CN 200610053176A CN 100569094 C CN100569094 C CN 100569094C
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China
Prior art keywords
cobalt
exchange resin
ion
cationic ion
resin
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Expired - Fee Related
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CN1911073A (en
Inventor
徐勇
胡彩虹
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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish
    • Y02A40/818—Alternative feeds for fish, e.g. in aquacultures

Abstract

The invention discloses a kind of cobalt-supplement forage additive and preparation and using method.It is a kind of cationic ion-exchange resin that contains active cobalt, and by weight percentage, the content of cobalt in cationic ion-exchange resin is 0.5～5.0%.Its preparation method adopts absorption, the ion-exchange reactions of cobalt salt and cationic ion-exchange resin, after filtration, dry, pulverizing makes the cationic ion-exchange resin that contains active cobalt.Because ion exchange resin is a kind of control slow-released carrier of function admirable, the cobalt of institute's load had the control slow releasing function, thereby improved the absorption rate of cobalt greatly.Cobalt-supplement forage additive of the present invention is easy to mix with feed, forms even disperse system, and is easy to use.

Description

A kind of cobalt-supplement forage additive and preparation and using method
Technical field
The present invention relates to a kind of cobalt-supplement forage additive and preparation and using method.
Background technology
The trophism of cobalt (Co) mainly is as VB 12Constituent, pass through VB 12To the healthy of animal and grow and work.Cobalt passes through VB 12Participate in Methyl transporters and glycometabolism, its activity form be methyl cobalamin and with the 5-adenosylcobalamin, the two is a coenzyme, can make the methionine demethyl.In addition, Co is to the metabolism of cobalt in the body, hemoglobin synthetic, and erythrocytic reach maturity and the release of mature cell etc. all has important function, Co can treat multiple anaemia, and is especially effective to low pigment cellule anaemia.Co also can influence the animal immune function.
Because ruminant VB 12The source mainly be synthetic by rumen microorganism, so Co is an indispensable mineral matter element in the daily ration to the healthy of ruminant domestic animal and grow significantly.It is reported that Co can promote ox to the utilization of urea with to cellulosic digestion, and improve the content of butterfat and lactoprotein in the speed of growth of ox and the milk.In the sheep feed, add cobalt chloride, can not only improve growing of sheep, can also stimulate the lamb growth, increase production of wool, Co also can stimulate the metabolism of cud, strengthens microorganism to cellulosic digestion power, thereby improves the digestion power of cattle and sheep to nutriment.Found to add the vigor that Co can increase enzyme in the ruminant.In addition, Co can also increase hemoglobin and erythrocytic concentration in the ruminant blood, strengthens the fertility of cattle and sheep.The cobalt formulation that is commonly used for interpolation has cobalt chloride, cobaltous sulfate, cobalt carbonate, cobalt acetate and cobalt oxide etc.
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-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 cobalt-supplement forage additive and preparation and using method.
Cobalt-supplement forage additive is a kind of cationic ion-exchange resin that contains active cobalt that adopts cobalt salt and cationic ion-exchange resin to be prepared from through absorption, ion-exchange reactions, and by weight percentage, the content of cobalt in cationic ion-exchange resin is 0.5～5.0%.
The preparation method of cobalt-supplement forage additive may further comprise the steps:
1) cationic ion-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) will contain the cobalt salt that the cobalt amount is a cationic ion-exchange resin weight 0.5～5.0%, be pre-configured to the aqueous solution of 0.1～1.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 3.0～6.0, 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 7.0～8.0; Wash 2～5 times, filter or centrifugal dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain cobalt-supplement forage additive.
The cobaltatess that use in the invention can be cobalt chloride, cobalt nitrate, cobalt acetate or cobaltous sulfate.Alkaline solution is that concentration is the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus of 0.5～5moL/L.
The using method of cobalt-supplement forage additive: admix in ox, sheep, livestock and poultry, the aquatic animal feed by following additive capacity in cobalt: ox 0.1～1.0mg/kg, sheep 0.2～1.5mg/kg, pig 0.1～1.0mg/kg, chicken, duck 0.1～0.5mg/kg, fish 0.2～1.0mg/kg, soft-shelled turtle 0.2～1.5mg/kg, shrimp 0.2～1.5mg/kg.
Advantage of the present invention is:
(1) utilize cationic ion-exchange resin can play the characteristics of exchange interaction with cation, cobalt is loaded in the cationic ion-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 cobalt of institute's load is had the control slow releasing function, thereby improved the absorption rate of cobalt greatly.
(3) cobalt-supplement forage additive of the present invention is easy to mix with feed, forms even disperse system, and is easy to use.
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 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 5 hours, drain after the acid solution with water rinse to neutral;
2) will contain the cobalt chloride that the cobalt 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 3.0, room temperature reaction 5 hours;
3) detection step 2) the 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 7.0; Wash filtering means dehydration 2 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain cobalt-supplement forage additive.By weight percentage, the content of cobalt in cationic ion-exchange resin is 0.5%.
Embodiment 2
1) (this product is equivalent to the U.S.: Amberlite200 with commercially available D001 macropore strong acid polystyrene cation conversion resin, West Germany: Lewaitet-SP120), 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;
2) will contain the cobalt nitrate that the cobalt amount is a cationic ion-exchange resin weight 5.0%, and 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 6.0, room temperature reaction 10 hours;
3) detection step 2) the 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 centrifugal dehydration 5 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain cobalt-supplement forage additive.By weight percentage, the content of cobalt in cationic ion-exchange resin is 5.0%.
Embodiment 3
1) (this product is equivalent to German LewatitCNP-80 with commercially available D113 macropore acidulous acrylic acid cation exchanger resin, 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;
2) will contain the cobalt acetate that the cobalt amount is a cationic ion-exchange resin weight 2.5%, and be pre-configured to the aqueous solution of 0.5mol/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 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 7.5; Wash filtering means dehydration 3 times;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain cobalt-supplement forage additive.By weight percentage, the content of cobalt in cationic ion-exchange resin is 2.5%.

Claims (2)

1. cobalt-supplement forage additive, it is characterized in that, it is a kind of cationic ion-exchange resin that contains active cobalt that adopts cobalt salt and cationic ion-exchange resin to be prepared from through absorption, ion-exchange reactions, by weight percentage, the content of cobalt in cationic ion-exchange resin is 0.5～5.0%, described cobalt salt is cobalt chloride, cobalt nitrate, cobalt acetate or cobaltous sulfate, and concrete preparation method's step is as follows:
1) cationic ion-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) will contain the cobalt salt that the cobalt amount is a cationic ion-exchange resin weight 0.5～5.0%, be pre-configured to the aqueous solution of 0.1～1.0mol/L, in stirring the resin that slowly adds step 1) down, the pH value of detection and conditioned reaction liquid is 3.0～6.0, 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 7.0～8.0; Wash 2～5 times, filter or centrifugal dehydration;
4) with filter cake oven dry under being lower than 70 ℃, the pulverizing of step 3) gained, obtain cobalt-supplement forage additive.
2. a kind of cobalt-supplement forage additive according to claim 1 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 0.5～5moL/L.
CNB2006100531769A 2006-08-28 2006-08-28 A kind of cobalt-supplement forage additive and preparation and using method Expired - Fee Related CN100569094C (en)

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CN101891582B (en) * 2009-05-21 2014-06-18 中国石油化工股份有限公司 Method for removing trace water from chloromethane
US10524489B2 (en) * 2017-07-12 2020-01-07 Zinpro Corporation Method and composition to control rumen release of cobalt to rumen bacteria for making vitamin B12

Citations (1)

* 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

Patent Citations (1)

* 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

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