CN101164432A - Molybdenum-tonifying feed additive and its preparation method - Google Patents

Molybdenum-tonifying feed additive and its preparation method Download PDF

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Publication number
CN101164432A
CN101164432A CNA2006100694817A CN200610069481A CN101164432A CN 101164432 A CN101164432 A CN 101164432A CN A2006100694817 A CNA2006100694817 A CN A2006100694817A CN 200610069481 A CN200610069481 A CN 200610069481A CN 101164432 A CN101164432 A CN 101164432A
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China
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molybdenum
exchange resin
anion
molybdate
feed additive
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胥保华
夏枚生
胡彩虹
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Shandong Agricultural University
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Shandong Agricultural University
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Abstract

The present invention discloses a molybdenum-supplementing feed additive and its preparation method. The described feed additive is an anion-exchange resin containing exchangeable molybdic acid radical, the molybdenum content in the anion-exchange resin is (by wt%) 1.0-8.5% Its preparation method is characterized by that it utilizes the feature of that the anion-exchange resin can produce exchange action with anion, so that it can make the molybdic acid radical ions be loaded in the anion-exchange resin. Because the anion-exchange resin is a controlled slowly-releasing carrier with excellent property, said anion-exchange resin possess the controllable slowly-releasing action for loaded molybdenum, so that the absorption utilization rate of molybdenum can be greatly raised. The molybdenum-supplencenting feed additive prepared by said invention has the characteristics of low-toxicity and high-efficiency, and is easily mixed with feed, can form uniform dispersion system, and is convenient for use.

Description

A kind of molybdenum-tonifying feed additive and preparation method
Technical field
The present invention relates to a kind of molybdenum-tonifying feed additive and preparation method.
Background technology
Molybdenum (Mo) is one of animal and plant growth trace elements necessary, extensively is present in soil, water, air, plant and the animal tissue.Molybdenum at first is familiar with by the animal scholar as a kind of poisonous element, and molybdenosis can make herds sheep and produce violent diarrhoea and faded by hair, is referred to as " Teart " disease.Therefore, people are devoted for years to the research that prevents and treats the aspect in the animal molybdenosis to molybdenum as noxious material always.
Molybdenum mainly is to depend on molybdenum enzyme (xanthine oxidase, aldehyde oxidase, sulfite oxidase) to participate in animal body metabolism, performance biological function.The enzyme that contains molybdenum plays catalytic action in the basic metabolism of carbon, sulphur, nitrogen cycle.The molybdenum enzyme is present in all organisms, participates in the metabolism of protein, sulfur-containing amino acid and nucleic acid.Molybdenum is as the main constituent of 3 kinds of different enzyme system xanthine oxidase/dehydrogenases, aldehyde oxidase and sulfite oxidases, it is active relevant with molybdenum content, but the oxidative metabolism of the purine compound in the xanthine oxidase catalysis animal body, the final uric acid that forms, this point is particularly important to poultry, can also the interior ferritin release of catalysis liver tap a blast furnace simultaneously, quicken the process that iron enters blood plasma, make the ferrous ion in the blood plasma be reduced into the monovalence iron ion very soon, and combine the formation transferrin rapidly with beta Globulin, enter liver, marrow.Sulfite oxidase can participate in the final step in the sulfur-containing amino acid oxidative pathway, and the catalysis methionine is degraded to pyruvic acid at last.Aldehyde oxidase participates in the transmission of endocellular electricity, participates in the oxidizing process of aldehyde in the body, makes aldehyde be converted into carboxylic acid, thereby removes the toxic action of the interior aldehyde that is produced of body to body.Molybdenum participates in the body metabolism by these enzymes and reaches trophism.
China belongs to and lacks the comparatively serious country of molybdenum, and most areas cause lacking in the plant feed molybdenum because of soil lacks the available state molybdenum.The reason of the scarce molybdenum of southern and northern feed is different, and available state molybdenum content is lower than scarce molybdenum critical concentration (0.15mg/kg) in the northern soil; Though molybdenum content is high but because mostly its soil is acid in the soils in south china, and under acid condition, forage plant is almost nil to the absorption rate of molybdenum.Molybdenum mainly is absorbed and used in alimentary canal with the molybdenum salt form of sexavalence in vivo, sexavalence water-soluble form such as sodium molybdate, ammonium molybdate etc. can be absorbed by animal preferably, the molybdenum that absorbs mainly retains in organs such as bone, skin, quilt hair and muscle, retains few in other histoorgans.
Add a certain amount of molybdenum in low molybdenum daily ration, gaining in weight of lamb is had remarkable result, this is because the cellulolytic ability of rumen bacteria strengthens, and has promoted the absorption of nutriment.And molybdenum is participated in the conversion of feed nitrate in the cud directly as the oxidasic constituent of ruminant tumor gastric microorganism nitrate; In addition, molybdenum has spread effect as the confactor of sulfite oxidase to the rumen microorganism metabolism, and this helps the digestion of ruminant to crude fibre class material.When the molybdenum level adds to 2.4mg/kg in the daily ration, significantly promote the growth of ruminant.Therefore, molybdenum element has special effect in the ruminant animal nutrition metabolism.For bird, plant with the hen molybdenum and exhaust, will and cause the congenital scarce molybdenum of chick by kind of egg transmission, make the chick growth hypoevolutism, defect ware rate height, strong young rate is low, and behind the interpolation sodium molybdate, chick growth is grown and is recovered normal in the chick daily ration; Through test, the weightening finish that fryer is mended the molybdenum group all is higher than group chicken group, and the broiler growth that adds molybdenum 5~7mg/kg daily ration improves 12.5% than control group, and gaining effect is extremely remarkable.Cause that easily dam is infertile when molybdenum in the feed lacks, male animal is sterile, and the cow in milk milk production reduces.The highest level of security of ox molybdenum is 5mg/kg.Laying hen showed as laying rate and significantly descends when molybdenum lacked, and death often takes place the embryo in the hatching of breeding eggs process.The death rate that lacks molybdenum daily ration group chick is far above mending the molybdenum group, and the meat chick is along with the increase of mending the molybdenum amount, and chicken group's the death rate descends.Molybdenum and other micro-antagonisms and collaborative can be alleviated other microelement deficiencies or reduce its toxicity, the correlation between molybdenum and the copper to livestock and poultry particularly ruminant health and produce quite important.
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 2Deng), 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-ExchangeResin Controlled 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 and a kind ofly have low toxicity, efficient, and be easy to the molybdenum-tonifying feed additive that mixes with feed.
Another object of the present invention is to provide a kind of preparation method of molybdenum-tonifying feed additive, the feed addictive of producing with this method has the control slow releasing function to the molybdenum of institute's load, can improve the absorption rate of molybdenum.
The invention provides a kind of molybdenum-tonifying feed additive, is a kind of anion exchange resin that contains commutative molybdate, and by weight percentage, the content of molybdenum in anion exchange resin is 0.1~5%.
The invention provides a kind of preparation method of molybdenum-tonifying feed additive, may further comprise the steps:
1) anion exchange resin is placed 1~2mol/L sodium hydroxide solution of 1~2 times of resin volume soaked 2~4 hours, drain behind the alkali lye with water rinse to neutral, 1~2mol/L hydrochloric acid solution with 1.5~3 times of resin volumes soaked 3~6 hours then, drained after the acid solution with water rinse to neutral;
2) will contain the molybdate that the molybdenum amount is an anion exchange resin weight 0.1~5%, be pre-configured to the aqueous solution of 0.01~1.0mol/L, with the flow velocity of 1~10mL/min by exchange column, finish after washing 2~5 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive.
The molybdate that uses in the invention can be sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate or ammonium molybdate.
Advantage of the present invention is:
(1) utilize anion exchange resin can play the characteristics of exchange interaction with anion, molybdate is loaded in the anion exchange resin, implementation method is easy, suitability for industrialized production.
(2) because ion exchange resin is a kind of control slow-released carrier of function admirable, the molybdenum of institute's load is had the control slow releasing function, thereby improved the absorption rate of molybdenum greatly.
(3) the prepared molybdenum-tonifying feed additive of the present invention has low toxicity, characteristics of high efficiency, and is easy to mix with feed, forms even disperse system, and is easy to use.
The specific embodiment
Anion exchange resin has the alkaline functional base for the strong alkalinity anion literary composition changes resin or weak-base anion-exchange resin, comprises strong basicity (quaternary ammonium group-N (CH 3) 3) and alkalescent (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.It is polystyrene or acrylic acid series that the anion literary composition changes resin matrix.
The present invention is further described in conjunction with following example.
Embodiment 1
1) be that (this product is equivalent to the U.S. to weak basic anion exchange resin: Amberlite IRA-68 with commercially available D311 macroporous acrylic; Germany: AP-49 D318), place the 1mol/L sodium hydroxide solution that waits the resin volume to soak 2 hours, drain behind the alkali lye with water rinse to neutral, the 1mol/L hydrochloric acid solution with 1.5 times of resin volumes soaked 3 hours then, drained after the acid solution with water rinse to neutrality;
2) will contain the sodium molybdate that the molybdenum amount is an anion exchange resin weight 0.1%, be pre-configured to the aqueous solution of 0.01mol/L, with the flow velocity of 1mL/min by exchange column, finish after washing 2 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive, and by weight percentage, the content of molybdenum in anion exchange resin is 0.1%.
Embodiment 2
1) (this product is equivalent to U.S. Amberlite IRA-400 with commercially available 201 * 7 (717#) strong basicity I type anion exchange resin, West Germany LewatitM500, Japan DiaionSA-10A), place the 2mol/L sodium hydroxide solution of 2 times of resin volumes to soak 4 hours, drain behind the alkali lye with water rinse to neutral, 2mol/L hydrochloric acid solution with 3 times of resin volumes soaked 6 hours then, drained after the acid solution with water rinse to neutral;
2) will contain the potassium molybdate that the molybdenum amount is an anion exchange resin weight 5%, be pre-configured to the aqueous solution of 1.0mol/L, with the flow velocity of 10mL/min by exchange column, finish after washing 5 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive, and by weight percentage, the content of molybdenum in anion exchange resin is 5%.
Embodiment 3
1) (this product is equivalent to the U.S.: Amberlyste IRA-94 with commercially available D301 macroreticular weakly base styrene series anion exchange resin; Amberlite IRA-93/94 DOWS MWA-1/66), place the 1.5mol/L sodium hydroxide solution of 1.5 times of resin volumes to soak 3 hours, drain behind the alkali lye with water rinse to neutral, 1.5mol/L hydrochloric acid solution with 2 times of resin volumes soaked 5 hours then, drained after the acid solution with water rinse to neutral;
2) will contain the ammonium molybdate that the molybdenum amount is an anion exchange resin weight 2.5%, be pre-configured to the aqueous solution of 0.5mol/L, with the flow velocity of 5mL/min by exchange column, finish after washing 3 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive, and by weight percentage, the content of molybdenum in anion exchange resin is 2.5%.
Embodiment 4
1) just commercially available D311 macroporous acrylic is that (this product is equivalent to the U.S. to weak basic anion exchange resin: Amberlite IRA-68; Germany: AP-49), place the 1mol/L sodium hydroxide solution of 2 times of resin volumes to soak 2 hours, drain behind the alkali lye with water rinse to neutral, the 1mol/L hydrochloric acid solution with 3 times of resin volumes soaked 6 hours then, drained after the acid solution with water rinse to neutral;
2) will contain the calcium molybdate that the molybdenum amount is an anion exchange resin weight 1%, be pre-configured to the aqueous solution of 0.1mol/L, with the flow velocity of 1mL/min by exchange column, finish after washing 2 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive, and by weight percentage, the content of molybdenum in anion exchange resin is 1%.

Claims (3)

1. a molybdenum-tonifying feed additive is characterized in that, it is a kind of anion exchange resin that contains commutative molybdate, and by weight percentage, the content of molybdenum in anion exchange resin is 0.1~5%.
2. the preparation method of a molybdenum-tonifying feed additive as claimed in claim 1 is characterized in that the step of method is as follows:
1) anion exchange resin is placed 1~2mol/L sodium hydroxide solution of 1~2 times of resin volume soaked 2~4 hours, drain behind the alkali lye with water rinse to neutral, 1~2mol/L hydrochloric acid solution with 1.5~3 times of resin volumes soaked 3~6 hours then, drained after the acid solution with water rinse to neutral;
2) will contain the molybdate that the molybdenum amount is an anion exchange resin weight 0.1~5%, be pre-configured to the aqueous solution of 0.01~1.0mol/L, with the flow velocity of 1~10mL/min by exchange column, finish after washing 2~5 times of exchange;
3) with step 2) anion exchange resin of the load molybdenum of gained is being lower than 70 ℃ of oven dry down, obtains molybdenum-tonifying feed additive.
3. the preparation method of a kind of molybdenum-tonifying feed additive according to claim 2 is characterized in that said molybdate is sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate or ammonium molybdate.
CNA2006100694817A 2006-10-22 2006-10-22 Molybdenum-tonifying feed additive and its preparation method Pending CN101164432A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102919568A (en) * 2012-10-24 2013-02-13 广东省昆虫研究所 Use of sodium molybdate in improvement of feed conversion rate of housefly larvae
CN108606164A (en) * 2018-04-11 2018-10-02 河南科技大学 A kind of poultry feed is with mending molybdenum additives, poultry molybdenum-tonifying feed and preparation method thereof
CN116022848A (en) * 2022-12-06 2023-04-28 西安诺博尔稀贵金属材料股份有限公司 By using molybdenum copper alloy scrap production of molybdic acid method for preparing sodium compound

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102919568A (en) * 2012-10-24 2013-02-13 广东省昆虫研究所 Use of sodium molybdate in improvement of feed conversion rate of housefly larvae
CN102919568B (en) * 2012-10-24 2013-12-25 广东省昆虫研究所 Use of sodium molybdate in improvement of feed conversion rate of housefly larvae
CN108606164A (en) * 2018-04-11 2018-10-02 河南科技大学 A kind of poultry feed is with mending molybdenum additives, poultry molybdenum-tonifying feed and preparation method thereof
CN116022848A (en) * 2022-12-06 2023-04-28 西安诺博尔稀贵金属材料股份有限公司 By using molybdenum copper alloy scrap production of molybdic acid method for preparing sodium compound

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Open date: 20080423