CN101497456B - Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use - Google Patents
Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use Download PDFInfo
- Publication number
- CN101497456B CN101497456B CN2008102181612A CN200810218161A CN101497456B CN 101497456 B CN101497456 B CN 101497456B CN 2008102181612 A CN2008102181612 A CN 2008102181612A CN 200810218161 A CN200810218161 A CN 200810218161A CN 101497456 B CN101497456 B CN 101497456B
- Authority
- CN
- China
- Prior art keywords
- acid
- copper chloride
- basic copper
- mixing vessel
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a method for preparing B type basic crystal copper chloride catalyzed and weathered by an acid and application thereof. The method comprises the following steps that: a, B type crystallized basic copper chloride is added into a mixing vessel, the mixing vessel is started, and the temperature in the mixing vessel is maintained to be between 30 and 100 DEG C; b, the acid is added in a spraying mode through a liquid adding device of the mixing vessel during the operation of the mixing vessel, and the spraying time is between 5 and 60 minutes; and c, the B type crystallized basic copper chloride and the acid are mixed for 5 to 100 minutes, and then the obtained product is naturally cooled to the normal temperature in the mixing vessel to obtain catalyzed and weathered crystallized basic copper chloride. The B type basic copper chloride catalyzed and weathered by the acid prepared by the method can be used as an animal feed additive. The B type basic copper chloride catalyzed and weathered by the acid has the characteristics of having better stability, not agglomerating when stored for a long time, refining particles, containing partial organic copper, being more favorable for the absorption and utilization of animal bodies, and the like.
Description
[technical field]
The present invention relates to the preparation method of compound, particularly relate to a kind of Preparation method and use of acid catalysis air slaking B crystal basic copper chloride.
[background technology]
Copper is that animal-feed must add additional micronutrient element.Chinese patent 200610060144.1 discloses the preparation method of a kind of Type B (Botallachite) crystal basic copper chloride; The prepared Type B crystal basic copper chloride of this method is because of having water insoluble but be prone to be dissolved in weakly acid soln, and good fluidity is easy to feed and cooperates; VITAMINs and lipid in the catalyzed oxidation feed hardly; The bioavailability of copper is high, and the promotes growth addition is little, helps advantages such as food safety and environment protection; And progressively replacing traditional copper sulfate to be used for fodder additives, herding circle at home and abroad obtains promoting as animal micronutrient element supplement.
The Type B crystalline state basic copper chloride stable technical process for preparing according to the method described above, production cost is low, but product particle thicker (its size distribution is at 30 to 300 microns).As animal feedstuff additive the time, particle is excessive certainly will to have prolonged its dissolution time in animal digestive tract, is unfavorable for that fodder additives is absorbed by animal body.
In production and practical application, find; The Type B crystal basic copper chloride is in storage process; Particularly higher at temperature, humidity is bigger, perhaps product not thorough drying, still contain under the situation of small amount of moisture; Occur the phenomenon that caking and color bleach easily, influenced its homodisperse in the feed process for preparation.Trace it to its cause, basic copper chloride because of contain ammonium chloride, storage temperature height, high humidity, pressurized and long time stored be the externalities that causes its caking, the unstable of himself crystalline structure is the internal factor of its caking.Through the X-ray diffractogram spectrum analysis contrast of the Type B crystal basic copper chloride of different periods of storage caking sample is found; Type B caking basic copper chloride is the variant to multiple crystal formation, multiple hydrate, multiple complex construction; Its change direction is uncertain, and changing factor is relevant with time, temperature, humidity etc., and period of storage is longer; The crystal formation matching degree is poorer, and promptly crystalline perfection is poorer.
Table 1 shows the X-ray diffractogram spectrum analysis correlation data of different period of storage basic copper chloride caking samples.
Table 1
Visible by above-mentioned X-ray diffractogram spectrum analysis: the Type B crystal basic copper chloride can take place to change slowly through long time stored its crystalline structure, and period of storage is longer, and the crystalline structure integrity is poorer.Because changing, crystalline structure causes size degradation reorganization between the particle; And the particulate of size degradation has certain activity and cohesive force; And the cracked volume of particle expands; Make to receive the stress that volumetric expansion produces and the extruding of own wt between the basic copper chloride particle, cause producing the cracked and caking phenomenon of crystalline particle.Be not difficult to find out thus, the Type B crystal basic copper chloride through the physicochemical change of the complicacy of long time stored generation cause its color by greenly bleach, the cracked weathering that is in the nature the Type B crystal basic copper chloride of the phenomenon of caking simultaneously of particle.
According to document (livestock and poultry ten big high-efficiency feed additives, the 160th page) report, animal is high than cupric sulfate pentahydrate to the absorption rate of some organic copper.Utilization ratio with cupric sulfate pentahydrate is 100%, and liver copper amount is an evaluation objective, and the relative biology utilization ratio that records other copper sources is: casein copper 170%, propionic acid copper 152%, venus crystals 142%, copper methionine 107%.Yet owing to there are problems such as raw materials cost height or technology difficulties be unresolved, organic copper is promoted on fodder additives at present as yet on a large scale.
[summary of the invention]
The present invention is intended to address the above problem, and provides a kind of stability better, does not long time storedly lump, and grain refine contains the part organic copper, more helps the preparation method of the acid catalysis air slaking B crystal basic copper chloride that animal body absorbs.
The present invention also aims to provide purposes by the prepared Type B crystal basic copper chloride of present method.
For realizing above-mentioned purpose, the present invention provides a kind of preparation method of acid catalysis air slaking B crystal basic copper chloride, and this method comprises the steps:
A, in mixing vessel, add the Type B crystal basic copper chloride, add-on is 20～80% of a mixing vessel volume, starts mixing vessel, and the temperature in the mixing vessel is remained on 30～100 ℃;
B, the liquid-adding device through mixing vessel in the mixing vessel operation process add acid with the mode of spraying, and the add-on of acid is 0.1～10% of a Type B crystal basic copper chloride mole number, and spray time is 5～60 minutes;
C, the Type B crystal basic copper chloride was mixed 5～100 minutes with acid, in mixing vessel, be cooled to normal temperature then naturally, Type B crystal basic copper chloride that must the catalysis weathering.
The reaction equation of this method is (is example with acetic acid) as follows:
2Cu
2(OH)
3Cl+2Hac＝Cu
2(OH)
3Cl-Cu(Ac)
2+H
2O
Among the step a, the molecular formula of Type B crystal basic copper chloride is Cu
2(OH)
3Cl, structure is a Botallackite, and particle diameter is 30～300 microns, and the weight percent content of its water content is 0.1～10%.
Among the step a, said mixing vessel is in the V-arrangement double-cone mixer of band spraying liquid feeding and heating unit, double-cone mixer, cone-type mixer, double worm mixer, duplex cone-type mixer, dry powder blender, the powder mixing machine any.
Among the step b, described acid is mineral acid or organic acid.Said mineral acid is any in hydrochloric acid, sulfuric acid, phosphoric acid, selenic acid, the selenous acid.Said organic acid is any in formic acid, acetic acid, propionic acid, Hydrocerol A, succsinic acid, fumaric acid, oxysuccinic acid, Sorbic Acid, fumaric acid, lactic acid, phenylformic acid, vinylformic acid, the oxalic acid.
Among the step c, the Type B crystal basic copper chloride is 15～30 hours with the natural temperature fall time of the mixture of acid.
The present invention also provides the purposes by the prepared Type B basic copper chloride of present method, and the acid catalysis air slaking B type copper chloride hydroxide of this method preparation is as animal feedstuff additive.
The present invention can prepare the complex body with multiple negatively charged ion copper compound through in the step b of aforesaid method, adding various acid, makes the copper complex body of preparation be used for fodder additives and has various additional functions.
For example, add organic acids such as formic acid, acetic acid, propionic acid, Hydrocerol A, succsinic acid, fumaric acid, oxysuccinic acid, Sorbic Acid, fumaric acid, lactic acid and can accelerate the growth in piglets growth, reduce the calf diarrhea; Add organic acids such as formic acid, propionic acid, Hydrocerol A, oxysuccinic acid, Sorbic Acid, fumaric acid, lactic acid and can suppress the feed moldy metamorphism; Adding Hydrocerol A, succsinic acid can promote the growth of chick, improve egg productivity and egg amount; Add mineral acids such as selenic acid, selenous acid micronutrient element selenium and the copper in the supplement feed simultaneously.
Contribution of the present invention is, it efficiently solve existing crystalline state basic copper chloride particle big (its size distribution is at 30 to 300 microns) and in storage process caking easily, be difficult to mix the use problem with other mineralogical compositions equably.Method technology of the present invention is simple, with low cost, and under damp and hot and the condition that adds acid, the crystalline state basic copper chloride with acid the chemical catalysis weathering takes place, the crystal grain cracking and puffing, and cracked is 0.1～50 micron particle.By rapid ageing, do not had activity and cohesive force by the cracked particle of acid catalysis rapid-weathering, therefore more stable, thus caking has no longer overcome the defective that the influence of crystalline state basic copper chloride caking is used.Particle after the weathering is by refinement, and the weak acid dissolution rate is accelerated greatly, and has reduced base contents.Prepared copper organic acid is better to the animal palatability, reduces hydrochloric acid in gastric juice consumption, has better bioavailability.
[description of drawings]
Fig. 1 is 200 times of metaloscope photos of Type B crystal basic copper chloride.
Fig. 2 is 500 times of metaloscope photos of the air slaking B type copper chloride hydroxide of method preparation of the present invention.
Fig. 3 is that the X-ray diffraction spectrum figure of the weathering basic copper chloride of method preparation of the present invention identifies contrast.
[embodiment]
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
One, the preparation of air slaking B crystal basic copper chloride:
Embodiment 1
Acetic acid catalysis air slaking B crystal basic copper chloride preparation: in volume is 500 liters V-arrangement bipyramid mixing vessel, add 500 kilograms of Type B crystal basic copper chlorides, the content of basic copper chloride is 96%; Moisture content is 4%; Open mixing machine, the mode with spraying in liquid-adding device adds 10 liters of 36% acetic acid, and spraying is reinforced to be carried out with batch mixing simultaneously; About 10 minutes of spray time; In temperature batch mixing 80 minutes under 60 ℃ the condition, cooling naturally then, packing promptly gets acetic acid catalysis air slaking B crystal basic copper chloride product after 1 day.
Embodiment 2
Lemon acid catalysis air slaking B crystal basic copper chloride preparation: in volume is 500 liters V-arrangement double-cone mixer, add 500 kilograms of Type B crystal basic copper chlorides, the content of basic copper chloride is 96%; Moisture content is 4%; Open mixing machine, the mode with spraying in liquid-adding device adds 5 liters of 30% aqueous citric acid solutions, and spraying is reinforced to be carried out with batch mixing simultaneously; About 10 minutes of spray time; In temperature batch mixing 80 minutes under 60 ℃ the condition, cooling naturally then, packing promptly gets lemon acid catalysis air slaking B crystal basic copper chloride product after 1 day.
Two, the pattern of weathering basic copper chloride and Type B crystal basic copper chloride, proportion and copper content analysis are to such as table 2:
Table 2
| The Type B crystal basic copper chloride | The weathering basic copper chloride | |
| Particle diameter | 100 microns | The 1-30 micron |
| Loose density | 1.82 | 1.0 |
| Copper content | 59.2％ | 58.5％ |
Visible by table 2, the weathering basic copper chloride is than 3～100 times of the particle size reduction of crystal basic copper chloride, and proportion reduces 1.82 times, and volume increases by 1.82 times.Therefore, the physical index of weathering basic copper chloride is more suitable for mixing with animal body in feed and absorbs.
Three, weathering basic copper chloride X-ray diffraction analysis:
Consult Fig. 3, the X ray diffracting spectrum analytical results is: crystal basic copper chloride is a Botallackite type basic copper chloride, and the weathering basic copper chloride is the mixtinite of Botallackite, atacamite and basic copper chloride hydrate.By rapid-weathering and rapid ageing, activity reduces this explanation basic copper chloride under the acid catalysis condition, and stability increases, and therefore no longer lumps.
Four, the dissolution rate simultaneous test in the weakly acidic solution:
Solubleness and dissolution rate in the weakly acidic solution of acoustic wind choline formula cupric chloride under the simulated animal gastric acid environment, measure solubleness and dissolution rate simultaneously by the Botallackite type basic copper chloride of the method preparation of No. 200610060144.1 patents:
Be dissolved in 1 liter of zero(ppm) water with 10 gram Hydrocerol As, 10 gram ammonium citrates, 2 milliliters of concentrated hydrochloric acids, be mixed with p H value and be 3.7 weakly acidic solution ammonium citrate buffered soln.
Analytical procedure is: accurately take by weighing the 0.1g basic copper chloride, and place triangular flask with cover, add 100 milliliters of weakly acidic solution ammonium citrate buffered soln respectively, 37 ± 1 ℃ of water bath with thermostatic control vibrations, measure its dissolution time.
Analytical results is: weathering basic copper chloride and Botallackite type basic copper chloride can both all dissolve; Both complete dissolution times were respectively 10 seconds and 30 seconds; Weathering basic copper chloride dissolution time shortens 2/3rds, shows that the weathering basic copper chloride is absorbed by animal than Botallackite more easily.
Claims (7)
1. the preparation method of an acid catalysis air slaking B crystal basic copper chloride is characterized in that, it comprises the steps:
A, in mixing vessel, add the Type B crystal basic copper chloride, add-on is 20～80% of a mixing vessel volume, starts mixing vessel, and the temperature in the mixing vessel is remained on 30～100 ℃, and the molecular formula of said Type B crystal basic copper chloride is Cu
2(OH)
3Cl, structure is a Botallackite, and particle diameter is 30～300 microns, and the weight percent content of its water content is 0.1～10%;
B, the liquid-adding device through mixing vessel in the mixing vessel operation process add acid with the mode of spraying, and the add-on of acid is 0.1～10% of a Type B crystal basic copper chloride mole number, and spray time is 5～60 minutes;
C, the Type B crystal basic copper chloride was mixed 5～100 minutes with acid, in mixing vessel, be cooled to normal temperature then naturally, Type B crystal basic copper chloride that must the catalysis weathering.
2. the method for claim 1 is characterized in that, among the step a, said mixing vessel is in the double-cone mixer of band spraying liquid feeding and heating unit, cone-type mixer, double worm mixer, the powder mixing machine any.
3. the method for claim 1 is characterized in that, among the step b, described acid is mineral acid or organic acid.
4. method as claimed in claim 3 is characterized in that, said mineral acid is any in hydrochloric acid, sulfuric acid, phosphoric acid, selenic acid, the selenous acid.
5. method as claimed in claim 3 is characterized in that, said organic acid is any in formic acid, acetic acid, propionic acid, Hydrocerol A, succsinic acid, fumaric acid, oxysuccinic acid, Sorbic Acid, lactic acid, phenylformic acid, vinylformic acid, the oxalic acid.
6. the method for claim 1 is characterized in that, among the step c, the Type B crystal basic copper chloride is 15～30 hours with the natural temperature fall time of the mixture of acid.
7. by the application of the acid catalysis air slaking B crystal basic copper chloride of the said method of claim 1 preparation as animal feedstuff additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102181612A CN101497456B (en) | 2008-12-12 | 2008-12-12 | Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102181612A CN101497456B (en) | 2008-12-12 | 2008-12-12 | Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497456A CN101497456A (en) | 2009-08-05 |
| CN101497456B true CN101497456B (en) | 2012-06-13 |
Family
ID=40944760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102181612A Active CN101497456B (en) | 2008-12-12 | 2008-12-12 | Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497456B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780971B (en) * | 2010-03-05 | 2013-01-16 | 广州科城环保科技有限公司 | Application of strong acid weak base salt or strong base weak acid salt in serving as anti-caking agent of type B basic copper chloride |
| CN101773218B (en) * | 2010-03-05 | 2012-09-19 | 广州科城环保科技有限公司 | Application of sinkaline used as B type alkali copper chloride anticaking agent |
| CN108185150B (en) * | 2017-12-18 | 2021-08-03 | 广州科城环保科技有限公司 | Basic copper chloride particulate matter and preparation method thereof |
-
2008
- 2008-12-12 CN CN2008102181612A patent/CN101497456B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497456A (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100698452B1 (en) | Development of ruminally protected nutrients and their utilization for milk and beef enrichment | |
| CN103694107B (en) | The preparation method of fodder additives beta-hydroxy-Beta-methyl Calcium Butyrate | |
| CN104206735A (en) | Microelement sucrose complex feed additive as well as preparation method and application thereof | |
| EP3841887A1 (en) | Rumen protected choline chloride microcapsule and preparatin method thereof | |
| CN101497456B (en) | Method for preparing acid catalysis air slaking B type copper chloride hydroxide and use | |
| CN107156469A (en) | Finished cattle expelling parasite stomach invigorating compound premixed feed licks brick | |
| CN101715886B (en) | Stabilized cysteamine growth promoting agent used for aquatic feeds and production method thereof | |
| CN102987081B (en) | Feed fragrance agent with feeding attraction function, and preparation method thereof | |
| CN108378205A (en) | One boar food and preparation method thereof | |
| CN105029128A (en) | Compound nutrient licking block feed suitable for mutton sheep | |
| CN104202999A (en) | Use of para nitro amino derivatives in feed for reducing me-thane emission in ruminants | |
| CN102657634B (en) | Nifuroxazide microcapsule powder and production method thereof | |
| CN111149940A (en) | Pet nutritional preparation for improving reproductive performance and preparation method thereof | |
| CN112521417B (en) | Preparation method and application of calcium glycerophosphate | |
| US5733590A (en) | Slow release non-protein nitrogen source for ruminant feed and process of making | |
| CN108684963A (en) | Small-peptide chelated manganese of a kind of nanometer for feed addictive and preparation method thereof | |
| CN102626179B (en) | Trace element and nutrient source premix and its preparation method | |
| SU1085496A3 (en) | Method for preparing fodder additive | |
| WO2010069109A1 (en) | Method and use of manufacturing botallachite trihydroxydicopper chloride effloresced by acid | |
| CN1568744A (en) | Feedstuff mildew-resistant additive | |
| CN101696175B (en) | Nickel threonine as well as preparation method and application thereof | |
| CN101780971A (en) | Application of strong acid weak base salt or strong base weak acid salt in serving as anti-caking agent of type B basic copper chloride | |
| JPH0697952B2 (en) | How to add liquid sugar to feed | |
| CN106306514A (en) | Health-care feed additive facilitating growth promotion of broilers and meat ducks and preparation method of health-care feed additive | |
| CN108541840A (en) | A kind of feed and preparation method thereof improving immunity of meat chickens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 518049 Guangdong city of Shenzhen province Futian District tail Meilin No. 181 Patentee after: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. Address before: The tail Meilin road 518049 Guangdong province Shenzhen city Futian District No. 181 Patentee before: Shenzhen Hazardous Waste Treatment Station Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Environmental Protection Technology Group Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: No. 181, Longwei, xiameilin, Futian District, Shenzhen, Guangdong 518049 Patentee before: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. |