CN1186989C - Chromium element feed additive using montmorillonite as carrier, its preparation method and application - Google Patents

Chromium element feed additive using montmorillonite as carrier, its preparation method and application Download PDF

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Publication number
CN1186989C
CN1186989C CNB021367353A CN02136735A CN1186989C CN 1186989 C CN1186989 C CN 1186989C CN B021367353 A CNB021367353 A CN B021367353A CN 02136735 A CN02136735 A CN 02136735A CN 1186989 C CN1186989 C CN 1186989C
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montmorillonite
chromium
feed additive
carrier
preparation
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CN1399903A (en
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叶瑛
沈忠悦
周玉航
朱晓燕
陈志飞
韩杰
冯璐珈
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention discloses a chromium element feed additive which takes smectite as carriers, a preparation method thereof and the application thereof. In the feed additive, smectite contains exchangeable chromium ions, and chromium elements account for 0.01 to 0.5 wt% of the smectite. The preparation method comprises the following procedures: trace element chromium which is required by lives is implanted into crystal lattices by utilizing the ion exchange capacity of clay minerals, chromium-carried montmorillonite containing active Cr<3+> ions is made, and solid powder is made by drying and milling the montmorillonite or drying the montmorillonite in a spray mode. The method has the advantages of simple technical process, low production cost and easy popularization. The chromium-carried montmorillonite feed additive which is made by the present invention can provide animal growth with the micronutrient element chromium by slow-release effect. The feed additive has the efficacy of enhancing animal immunity, promoting animal growth and development, effectively improving feed utilization rate, improving the lean meat percentage of midsections and the laying rate of domestic fowls, etc. The additive can be used as the feed additive of livestock, domestic fowls and fish.

Description

With the montmorillonite chromium element feed additive and preparation method thereof and the usage of carrier
Technical field
The present invention relates to a kind of is the chromium element feed additive and preparation method thereof and the usage of carrier with the montmorillonite.
Background technology
Chromium is one of trace element essential in the humans and animals body, and it mainly shows in the following areas the contribution of animal physiological function:
1) Cr 3++Ion is the part in glucose tolerance factor (GIF) activated centre, and it and insulin acting in conjunction make that glycogen is synthetic in the body increases, and the blood sugar mobility improves, thereby makes glucose transfer to other tissue fast and be utilized from liver.
2) by improving the activity of insulin, regulate the animal fat metabolism, improve the blood fat situation, make cholesterol and the reduction of triglyceride content in the meat product, help edible healthy.
3) chromium can promote that amino acid enters cell, improves the synthetic ratio of protein, makes nutriment in the animal body be used for the muscle of growing more, rather than is transformed into fat, therefore can improve efficiency of feed utilization greatly, and obviously increase the lean meat percentage of trunk.
4) anti-stress ability of raising animal.For the animal that is in the adverse environment, as long-distance transportation, noise jamming, cause of disease attacks, and environment temperature, humidity are too high or too low etc., and mending chromium can reduce the serum cortisol concentration of animal, thereby improves the anti-stress ability of animal.
5) strengthen immunity.In the chromium immune response in animal body, play a part immune-regulating factor,, strengthen the premunition and the adaptability of body by to immunoreactive adjusting.
6) improve dam litter size and poultry laying rate.After being in the sow benefit chromium of breeding period, the nest litter size all is significantly improved with the young litter weight of living.Add chromium in the egg fowl daily ration, its laying rate also is significantly increased, and the chromium content in the yolk improves nearly one times.Contain chromium higher " health care egg " and can reduce the human risk of suffering from cardiovascular disease and diabetes.
Chromium has+6 ,+3 and+2 three kinds of valence states.Cr wherein 6+Bio-toxicity is big, Cr 2+Stable inadequately, they all are not suitable for use in animal and mend chromium.The trivalent inorganic chromium is cheap, and security is higher, and solubility is good, but absorptivity is low in animal body, only is 0.5~2%, even lower.Animal is mended chromium and adopts the trivalent Organic Chromium more at present, as nicotinic acid chromium, yeast chromium, chromium picolinate, chelating amino acids chromium, protein chromium etc.The biological absorption of Organic Chromium is higher, reaches as high as 25~30%, and validity is more than ten times of inorganic chromium.But Organic Chromium costs an arm and a leg, and the effect of part Organic Chromium still can not be affirmed.
Summary of the invention
The purpose of this invention is to provide a kind of is the chromium element feed additive and preparation method thereof and the usage of carrier with the montmorillonite.
Of the present invention is that the chromium element feed additive of carrier is a kind of montmorillonite that contains commutative chromium ion with the montmorillonite, and by weight percentage, the content of chromium element in montmorillonite is 0.01~0.5%.
This is that the preparation method of the chromium element feed additive of carrier may further comprise the steps with the montmorillonite:
1) separates purifying montmorillonite according to a conventional method, with montmorillonite and weight is the sodium salt mixing of montmorillonite 5~15%, adding water stirs, carry out ion-exchange reactions, centrifugal then or filtering means dehydration is after water cleans, adding water again stirs, make concentration and be 3~20% na-montmorillonite suspension ore pulp, detect and regulate the pH value of ore pulp, making slurry pH is 4.5~6.0;
2) with chrome content be the chromic salts of montmorillonite weight 0.01~0.5%, the water-soluble solution that is configured to, and splash into several diluted acids and make the solution acidifying;
3) when stirring, slowly pour the chromium salt solution that configures into ore pulp, carry out ion-exchange reactions;
4) the pH value of detection ore pulp is regulated with alkaline solution, and making slurry pH is 6.5~8.5;
5) with methods such as precipitation, centrifugal or press filtrations, make pulp dewatering;
6) shine dry or dry being lower than under 80 ℃ of temperature the step 5) gains are cool naturally, be ground to less than 300 orders, obtain water content less than 10% powder, perhaps the step 5) gains are added maximum 5% dispersant, adding water stirs, make 10~30% ore pulp, obtain water content less than 10% powder with conventional spray drying process.
In preparation method of the present invention:
Said montmorillonite is sodium base, calcium base, magnesium base montmorillonite.Sodium salt is selected sodium chloride, sodium nitrate, sodium sulphate or its hydrate for use.Chromic salts is selected one or more in the hydrate of chromium chloride, chromic nitrate and chromium sulfate or these salts for use.Said alkaline solution is Ca (OH) 2, NaOH, Na 2CO 3, NaHCO 3Deng solution, dispersant is a sodium tripolyphosphate, tetrasodium pyrophosphate, one or more in the sodium lignosulfonate.
If adopt spray drying process, its spray dryer EAT is controlled at 150~180 ℃, 60~80 ℃ of discharging opening temperature.
The chromium element feed additive that said method is made is used for feed, to contain the chromium element be 0.5~3 milligram the volchonskonite that carries by adding in the per kilogram feed, generally moisture higher green and rough feeds is added the volchonskonite that carries that contains 0.5~1 milligram of chromium, mixed feed that water content is lower and concentrated feed add the volchonskonite that carries that contains 1~3 milligram of chromium.Should be in the external packing of product, so that the user calculates the consumption of additive before use with the content distinguishing mark of chromium element.
Carrying volchonskonite can add in the feed with different modes.The volchonskonite that carries of powdery directly can be admixed in the feed, also can be sprayed on the feed carrying the suspension that volchonskonite is configured to debita spissitudo.No matter which kind of mode of employing all should make additive and feed mix, this raises particularly important to concentrating type.
Advantage of the present invention is:
1) utilize the cation exchange capacity (CEC) of natural montmorillonite to carry trivalent chromic ion, production cost is low;
2) the compatibility height of carrier mineral montmorillonite and animal gastrointestinal tract mucous membrane has improved Cr greatly 3+Ion absorptivity has in animal body also reduced simultaneously the environment residual quantity;
3) slowly releasing effect of montmorillonite has improved Cr 3+The safety in utilization of ion;
4) carry volchonskonite and be easy to mix, form even disperse system with feed, easy to use.
The specific embodiment
The natural montmorillonite (having another name called bentonite) of separate purifying among the present invention is well-known, and it comprises that pulverizings, making beating make suspension, classification collection less than the particle of 2 μ etc.This highly purified montmorillonite is the clay mineral of a kind of light green color, light yellow tool layered crystal structure.Separate purification process and can select conventional mining equiment for use.
Ion-exchange reactions is carried out in two steps, and the first step is used sodium salt solution, makes the Na in the solution +Ca in the ion exchange montmorillonite mineral lattice 2+, Mg 2+With other interlayer cation, said sodium salt is sodium chloride, sodium nitrate, sodium sulphate.The requirement of sodium salt use amount is not very strict, and generally speaking, the sodium salt consumption is not less than 8% of montmorillonite dry weight.Na +The ion-exchange reactions of ion and montmorillonite can at room temperature be carried out, and if any cheap thermal source, also can heat ore pulp.Heating can be shortened the reaction time.
Second step was used chromium salt solution, made the Cr in the solution 3+Na in the ion exchange montmorillonite mineral lattice +With other interlayer cation, said chromic salts can be selected one or more in chromium chloride, chromic nitrate and the chromium sulfate for use, and the present invention recommends to use chromium chloride.The chromic salts consumption should make the chromium element be equivalent to 0.01~0.5% of montmorillonite weight, and recommendation is 0.1%.Before using chromic salts is dissolved in the water fully, the purpose that splashes into diluted acid be make solution-stabilized.
In manufacturing process of the present invention, it is not very strict that the water yield that relevant step is added requires, and under the prerequisite that equipment such as stirring, mixing and spray-drying can run well, should reduce water, to reduce production costs as far as possible.Stirring and mixing can be selected conventional equipment for use, and the time limit of mixing is advisable can form obviously uniform slurry.
The pH value of control and regulation ore pulp is one of key of the present invention.Before chromium salt solution added ore pulp, should detect the pH value of ore pulp, too high as pH, can use watery hydrochloric acid or other diluted acid, pH values of pulp is adjusted to below 6.0, in order to avoid chromic salts generation flocculation sediment.Chromium salt solution should slowly add ore pulp when stirring slowly.
Cr 3+Can at room temperature carry out with the ion-exchange reactions of montmorillonite,, also can heat ore pulp if any cheap thermal source.Heating can be shortened the reaction time.
Cr 3+After ion-exchange reactions finishes, should detect the pH value of ore pulp once more,, make pH values of pulp be not less than 6.5 if its pH<6.5 then add an amount of alkaline solution.Ca (OH) is used in suggestion 2Solution, promptly limewash is beneficial to environmental protection.The purpose that this regulates the pH value is to make Cr remaining in the solution 3+Ion precipitation is in order to avoid contaminated environment.After regulating pH, should be once more that flowsheet of slurry agitation is even.
The dewatering process of ore pulp can be suited measures to local conditions, and selects for use filter cloth filtration, sedimentation basin, centrifuge or filter press to dewater.
The dehydration back should notice that bake out temperature must not surpass 90 ℃ if use the drying plant drying, preferably is controlled at below 80 ℃, and the too high meeting of temperature undergoes phase transition montmorillonite, loses cation exchange capacity (CEC), Cr 3+Ion also loses activity thereupon.
Year volchonskonite after the oven dry is hard bulk, can select for use conventional mining equiment crushing grinding to granularity to be not more than 300 orders.Be final products after the pack.
As select spray-drying for use, then need ore pulp slurrying again, and add dispersant having dewatered.Be applicable to that dispersant requirement of the present invention is not very strict.The dispersant of recommending to use is a sodium tripolyphosphate, one or more in tetrasodium pyrophosphate and the sodium lignosulfonate.The purpose that adds dispersant is the viscosity that reduces slurry, makes the spray-drying of high concentration slurry become possibility, thereby reduces energy consumption for drying.Spray dried products is a kind of runny pressed powder.Be applicable to that spray drying device of the present invention is routinely, technical is well-known.
Further specify the present invention below in conjunction with instantiation.
Embodiment 1:
With the montmorillonite is the preparation method of the chromium element feed additive of carrier, may further comprise the steps:
1) takes by weighing 10Kg and separate the ca-montmorillonite of purifying, add water 90Kg, add 1Kg sodium chloride, in agitator, stir with conventional method; At room temperature carried out ion-exchange reactions at least six hours, stir therebetween for several times, centrifugal dehydration then, after the water cleaning, stirring, centrifugal 1~2 time, adding 90Kg water again stirs, make concentration and be 10% na-montmorillonite suspension ore pulp, detect and regulate the pH value of ore pulp, making slurry pH is 5.5;
2) take by weighing 30.5 gram CrCl 3(containing chromium element 10 grams), dissolve in the premium on currency, in solution, splash into several watery hydrochloric acid, stir.
3) when stirring, CrCl3 solution is slowly poured in the agitator that fills ore pulp.Allow ore pulp and chromium-containing solution in agitator, react six hours, during stirred 3~5 minutes every one hour so that ore pulp keeps suspended state.
4) pH that records ore pulp with pH meter is 6.0.Add 500 milliliters of limewash clear liquids, stir, recording pH again is 7.0.
5) ore pulp leaves standstill diel in agitator, makes the montmorillonite natural sedimentation, absorbs supernatant liquor with siphonage, and sediment is poured on further dehydration on the filter cloth.
6) ore pulp after will dewatering is divided into fritter with shredding machine or spades, temperature be no more than oven dry under 80 ℃ of environment, broken, grind, make product granularity less than 300 orders, pack.The chromium constituent content is 0.1% in the product at this moment.
Embodiment 2:
Take by weighing 10Kg mixed feed or concentrated feed, pour in the mixer.Take by weighing the chromium element feed additive of 20g, evenly be sprinkling upon on the feed, open mixer, additive and feed are mixed get final product by the preparation of embodiment 1 method.Chromium constituent content in the feed is 2mg/Kg at this moment.
Embodiment 3:
Take by weighing the chromium element feed additive of 10g by the preparation of embodiment 1 method, insert in the domestic food mixer, add one liter in water, start stir about one minute is made suspension.The 20Kg greenfeed evenly is sprinkling upon on the clean ground, above-mentioned suspension evenly is sprayed on the greenfeed with clean agricultural atomizer, can use after drying.Chromium constituent content in the greenfeed is 0.5mg/Kg at this moment.
The invention provides a kind of is the chromium element feed additive and preparation method thereof of carrier with the montmorillonite.The raw material sources that this invention relates to are abundant, and preparation method and technological process are simple, and low production cost is easy to promotion and implementation.The chromium element feed additive that makes based on the present invention, can be widely used in the raising of various domestic animals, poultry and fish, for above-mentioned animal is replenished teleorganic chromium element, has the raising efficiency of feed utilization, promotion is grown, strengthen animal immunizing power and anti-stress ability, improve effects such as carcass lean meat percentage and bird laying rate.

Claims (9)

1. one kind is the chromium element feed additive of carrier with the montmorillonite, it is characterized in that it is a kind of montmorillonite that contains commutative chromium ion, and by weight percentage, the content of chromium element in montmorillonite is 0.01~0.5%.
2. according to claim 1 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that it may further comprise the steps:
1) separates purifying montmorillonite according to a conventional method, with montmorillonite and weight is the sodium salt mixing of montmorillonite 5~15%, adding water stirs, carry out ion-exchange reactions, centrifugal then or filtering means dehydration is after water cleans, adding water again stirs, make concentration and be 3~20% na-montmorillonite suspension ore pulp, detect and regulate the pH value of ore pulp, making slurry pH is 4.5~6.0;
2) with chrome content be the chromic salts of montmorillonite weight 0.01~0.5%, the water-soluble solution that is configured to, and splash into several diluted acids and make the solution acidifying;
3) when stirring, slowly pour the chromium salt solution that configures into ore pulp, carry out ion-exchange reactions;
4) the pH value of detection ore pulp is regulated with alkaline solution, and making slurry pH is 6.5~8.5;
5) with methods such as precipitation, centrifugal or press filtrations, make pulp dewatering;
6) shine dry or dry being lower than under 80 ℃ of temperature the step 5) gains are cool naturally, be ground to less than 300 orders, obtain water content less than 10% powder, perhaps the step 5) gains are added maximum 5% dispersant, adding water stirs, make the ore pulp of 10-30%, obtain water content less than 10% powder with spray drying process.
3. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that said montmorillonite is sodium base, calcium base, magnesium base montmorillonite.
4. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that said sodium salt is sodium chloride, sodium nitrate, sodium sulphate or its hydrate.
5. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that said chromic salts is the hydrate of chromium chloride, chromic nitrate and chromium sulfate or these salts.
6. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that said alkaline solution is Ca (OH) 2, NaOH, Na 2CO 3, NaHCO 3Solution.
7. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that said dispersant is a sodium tripolyphosphate, tetrasodium pyrophosphate, one or more in the sodium lignosulfonate.
8. according to claim 2 is the preparation method of the chromium element feed additive of carrier with the montmorillonite, it is characterized in that its spray dryer EAT is controlled at 150~180 ℃, 60~80 ℃ of discharging opening temperature if adopt spray drying process.
9. claim 1 is described is that the chromium element feed additive of carrier is used for feed with the montmorillonite, it is characterized in that in the per kilogram feed, and adding and containing the chromium element is 0.5~3 milligram the volchonskonite that carries.
CNB021367353A 2002-08-27 2002-08-27 Chromium element feed additive using montmorillonite as carrier, its preparation method and application Expired - Fee Related CN1186989C (en)

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CN1186989C true CN1186989C (en) 2005-02-02

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Publication number Priority date Publication date Assignee Title
CN101214007B (en) * 2008-01-09 2010-09-15 浙江大学 Method for preparing controlled and sustained-release type lysine for marine lives
CN105580987B (en) * 2014-10-23 2019-08-30 麦闪石G.M.株式会社 Feed organic coating Porous particle and preparation method thereof
CN106858063A (en) * 2017-03-04 2017-06-20 杨克泉 A kind of montmorillonite absorbent-type Choline Chloride released fodder additive and preparation method thereof
CN115024392A (en) * 2022-06-15 2022-09-09 长沙傲鑫生物工程有限公司 Preparation method for loading metal ion compound by using non-metallic mineral
CN115053937A (en) * 2022-06-20 2022-09-16 浙江惠嘉生物科技股份有限公司 Preparation method of chromium nicotinate nano dispersion preparation

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