CN108084018A - A kind of manufacturing method of feed copper citrate and its application - Google Patents
A kind of manufacturing method of feed copper citrate and its application Download PDFInfo
- Publication number
- CN108084018A CN108084018A CN201810023685.XA CN201810023685A CN108084018A CN 108084018 A CN108084018 A CN 108084018A CN 201810023685 A CN201810023685 A CN 201810023685A CN 108084018 A CN108084018 A CN 108084018A
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- Prior art keywords
- copper
- citrate
- feed
- copper citrate
- manufacturing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/22—Compounds of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
Abstract
Manufacturing method and its application the invention discloses a kind of feed copper citrate, by the way that sodium citrate and copper sulphate are put into respective head tank, add in isometric soft water simultaneously, and open steam valve, it dissolves by heating, open reaction kettle, open simultaneously sodium citrate and copper-bath valve switch, lasting stirring, the substance of generation is placed in container and is cooled to room temperature, it carries out separating and filtering and is washed with water, absorption water is sloughed into filter cake drying and partially crystallizable water can obtain feed copper citrate.The present invention also provides application scheme of the copper citrate in livestock-raising, realized by adding the premix containing copper citrate when feeding according to the weight of animals.It is safe and reliable that the present invention is prepared copper citrate, and preparation process is simple, is suitble to scale application.
Description
Technical field
The invention belongs to livestock-raising field of feed, and in particular to a kind of manufacturing method of feed copper citrate and
It is applied.
Background technology
Feed industry has become indispensable important industry in Chinese national economy, it is the animalities such as meat, egg, milk food
The basis of product production, to uplifting the people's living standard, ensureing that social stability has played irreplaceable role.But recently as
The fast development of aquaculture and the continuous progress of science and technology, the use of antibiotic and high-copper is to animal itself, ecological environment and livestock products
The threat aggravation of product, safety, the high-quality basic demand for having become animal husbandry development, it is joyous that the low copper safe feed of nonreactive receives industry
It meets.
Copper participates in the composition of body, while is also a variety of enzyme (copper-zinc superoxide discriminations as a kind of necessary trace element
Change enzyme, ceruloplasmin etc.) important composition ingredient.Research shows that the copper sulphate of high dose has and promotes growth of animal, improves and raises
Expect the effect of transfer efficiency.It is modernizing, in the pig production of scale, grice diarrhoea is relatively common, and high-copper is young to reducing
The diarrhea tool of pig has certain effect.However the copper of high dose can remain in pig body in feed, and harm may be brought to pig.
Currently used Inorganic Copper (the copper sulphate, basic copper chloride etc.) absorptivity of feed addictive in vivo is very low, this can be caused greatly
Amount copper is discharged into environment, causes measuring copper in environment.In contrast, organic copper is relatively stablized, in electroneutral, height
It spends solvable, its structural intergrity can be maintained in animal alimentary canal and reaches intestinal absorption site, so as to be efficiently absorbed.This
It means that while can reach the growth performance similar to high dose Inorganic Copper with the organic copper of less dosage, reduces to ring
Border is polluted, and is reduced the illeffects to pig, is improved the security of pork.
There is research to think, citric acid can be used as ligand, and chelation occurs with minerals.At 25 DEG C, citric acid with
The complexation constant (Igk) of copper ion is 14.2, thus citric acid and copper ion can form that stable, biological value is higher
Complex, so as to promote absorption of the animal intestinal tract to mineral element.At present, the manufacture of feed copper citrate is not yet found
Method and its security performance introduction.On food pharmaceutical grade copper citrate, common production method is to utilize copper carbonate and oxidation
Copper citrate is made for raw material and edible citric acid reaction in copper, but this method is not suitable for manufacturing feed copper citrate,
Because copper carbonate is insoluble in water, is not reacted with water, pure copper carbonate can not be obtained, can be only formed mixture;And copper oxide category
In noxious material, if making raw material with copper oxide, high risks may be carried out to direct labor's health care belt, wrongly take or suck and is a large amount of
Copper oxide dust be present with shiver, body temperature rise, while with respiratory tract symptom, Long Term Contact may cause respiratory tract
And eye conjunctiva stimulation, nosebleed epistaxis, schneiderian membrane blutpunkte or ulcer or even perforation of nasal septum and dermatitis.
The content of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of manufacturers of feed copper citrate
Method, and test evaluation is carried out to its security performance.
In order to achieve the above object, the technical solution adopted by the present invention is used using sodium citrate and copper sulphate synthetic diet
Copper citrate.
Specifically, a kind of manufacturing method of feed copper citrate, comprises the following steps:
(1) sodium citrate and copper sulphate are put into respectively in respective head tank, while adds in isometric soft water, and opened
Steam valve dissolves by heating;
(2) reaction kettle is opened, opens simultaneously sodium citrate and copper-bath valve switch, it is lasting to stir, make citric acid
Sodium fully reacts in a kettle with copper sulphate;
(3) substance of generation is placed in container and be cooled to room temperature, carry out separating and filtering and be washed with water, filter cake is dried
Dry, feed copper citrate can be arrived by sloughing absorption water and partially crystallizable water.
The copper sulphate and the mass ratio of sodium citrate are 1:1~1:3, it is preferred that the copper sulphate and citric acid
The mass ratio of sodium is 1:2.
Heating for dissolving condition is to be carried out at 80 DEG C in the step (1).
Persistently stirring needs to carry out under 80 DEG C of constant temperature in the step (2).
Drying specific location dries 1h under the conditions of 100 DEG C in the step (3).
Application of the copper citrate that preparation method of the present invention obtains in livestock-raising feed is prepared.Its pass through by
Copper citrate is mixed with conventional solid feed, i.e. available according to the customary preparation methods of this field, wherein the lemon
The usage amount of sour copper is no more than 37.5mg/kg weight.
The present invention also provides application of the copper citrate in livestock-raising, by according to weight when feeding
The premix containing copper citrate is added to realize.It is added in right amount according to the growth of animal time when feeding, under normal circumstances
No more than 37.5mg/kg weight.
The beneficial effects of the present invention are:
(1) virose or unstable raw material is not used to produce copper citrate, because without being made to operating personnel
Into actual bodily harm, while contaminant problem existing for conventional production process is avoided, improve product safety performance.
(2) feed is only Na with the by-product in copper citrate production process2SO4。Na2SO4Feed can be recycled as to add
Add agent, thus it is entire production process green, environmental protection, nonhazardous, pollution-free.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's all other embodiments obtained without making creative work, belong to this hair
The scope of bright protection.
Embodiment 1
The copper citrate production of five batches is carried out continuously, by ingredient proportion provided by the invention and production temperature, time
Etc. parameters, record yield.
Preparation method:
Sodium citrate and copper sulphate are put into respectively in respective head tank, the quality proportioning point of copper sulphate and sodium citrate
It Wei 1:1、1:1.5、1:2、1:2.5、1:3, while isometric soft water is added in, and steam valve is opened, added at 80 DEG C
Heat of solution opens reaction kettle, opens simultaneously sodium citrate and copper-bath valve switch, persistently stirred under 80 DEG C of constant temperature,
Sodium citrate is made fully to be reacted in a kettle with copper sulphate, the substance of generation is placed in container and is cooled to room temperature, is divided
From filtering and being washed with water, filter cake is dried into 1h under the conditions of 100 DEG C, feed use can be arrived by sloughing absorption water and partially crystallizable water
Copper citrate.As a result such as table 1:
1 copper citrate product yield of table
By table 1 as it can be seen that producing feed copper citrate using copper sulphate and sodium citrate, the yield of product can be made
It is higher, wherein when the quality proportioning of copper sulphate and sodium citrate is 1:2 yield highests.
Application test evaluation is carried out to the copper citrate that the present invention is prepared with reference to specific embodiment.
Embodiment 2
1. tested material:Copper citrate.
2. experimental animal:SD rats 96 (half male and half females), 180~220g of weight.
3. poisoning dosage and grouping:By trial test determine poisoning dosage for 3471mg/kg weight, 2670mg/kg weight,
2054mg/kg weight, 1580mg/kg weight, 1215mg/kg weight and 935mg/kg weight.96 SD rats are randomly divided into 6
Group, every group 16 (half male and half female) are tested.
4. contamination method and volume:Tested material copper citrate is configured to mix with 0.5% carboxymethylcellulose sodium solution
Liquid contaminates to SD rats using oral administration by gavage, and gavage volume is respectively 2mL/100g weight.
5. observation index:General performance, poisoning symptom, death toll and the death time of SD rats are observed after contamination, and it is right
Rat cadavers carry out dissect, make a record.Observing time is 2 weeks, as a result such as table 2.
The death rate (%) after 2 copper citrate SD exposed rats of table
As shown in table 2, SD rats occur poisoning symptom during experimental observation and show as dull behavior, movable reduction, food
Be intended to decline, general tremor, flock together, chilly, myosis, excrement are shapeless and in green, diarrhea, more than extremely with poisoning dosage
Exacerbation trend is presented in rise.The dead mouse of dissection, opens the visible gastrointestinal tract of abdomen in apparent expanded state, includes blackish green content.
The rat of high dose group starts death in gavage 2h, other dosage rats start death generally after 24~48h.
By 3471mg/kg weight, 2670mg/kg weight, 2054mg/kg weight, 1580mg/kg weight, 1215mg/kg bodies
Weight and 935mg/kg body weight doses are orally contaminated, and are tested through 4 repetitions, SD rats deaths rate is within the experimental observation time limit
100.00%th, 87.50%, 81.25%, 56.35%, 43.75% and 0%, SD rats death situation it is as shown in table 2.According to bandit
Family name (Korbor) method can be calculated LD50For 1504mg/kg weight, standard is mistaken for 0.02, and confidence interval is 1354~1692mg/kg
Weight.
Embodiment 3
1. tested material:Copper citrate
2. experimental animal:SD rats 80, half male and half female, 110~130g of weight.
3. poisoning dosage and grouping:Experiment set 150mg/kg weight (height), 75mg/kg weight (in), 37.5mg/kg weight
(low) three dosage groups, separately set a negative control group.Every group of 20 rats (half male and half female) are tested.
4. the preparation and contamination of tested material:The consumption of 30 days feed for nursing is calculated by the 8% of weight, and copper citrate is added
Pellet is made into full price powder, experiment rat, continuous raising 30 days are given with free choice feeding.
Influence of the copper citrate to SD rats average weight gain and overall average weightening (g/ days /) is shown in Table 3.
Table 3 feeds influence of 30 days copper citrates to SD rats average weight gain and overall average weightening (g/ days /)
As shown in Table 3,1~7 day when, addition 150mg/kg weight (high dose), 75mg/kg weight (middle dosage) and
The average weight gain pole of 37.5mg/kg weight (low dosage) copper citrate male SD rat is significantly higher than negative control group (P<
0.01), but the average weight gain pole of female sd inbred rats is markedly inferior to negative control group (P<0.01);At 8~14 days, addition
The average weight gain pole of 150mg/kg weight (high dose) copper citrate male and female SD rats is markedly inferior to negative control group (P<
0.01);At 15~21 days, the average weight gain for adding 75mg/kg weight (middle dosage) copper citrate male SD rat is extremely significantly low
In negative control group (P<0.01);At 22~30 days, addition 150mg/kg weight (high dose) copper citrate male SD rat
Average weight gain pole is significantly higher than negative control group (P<0.01);Add 150mg/kg weight (high dose) and 75mg/kg weight (in
Dosage) copper citrate female sd inbred rats overall average weightening pole be markedly inferior to negative control group (P<0.01).
Embodiment 4
On the basis of embodiment 3, influence of the copper citrate to SD rat routine blood indexes is further studied, is specifically shown in Table
4。
Table 4 feeds influence of 30 days copper citrates to SD rat routine blood indexes
As shown in Table 4, the male female SD of 150mg/kg weight (high dose) and 75mg/kg weight (middle dosage) copper citrate is added
The leukocyte count pole of rat is markedly inferior to negative control group (P<0.01);Add 150mg/kg weight (high dose) and 75mg/
The red blood cell number of kg weight (middle dosage) copper citrate female sd inbred rats is markedly inferior to negative control group (P<0.05);Addition
The content of hemoglobin of 150mg/kg weight (high dose) and 75mg/kg weight (middle dosage) copper citrate female sd inbred rats is extremely aobvious
It writes ground and is less than negative control group (P<0.01).
In conclusion by copper citrate with 150mg/kg weight (high dose), 75mg/kg weight (middle dosage) and
37.5mg/kg weight (low dosage) Three doses, which are added in full price powder, is made pellet, is given and tested with free choice feeding
Rat carries out 30 days feeding trials, as a result as follows:
1st, within the experimental observation time limit, each dosage group SD rat general behaviors are acted normally, no poisoning and death condition.
Pole significantly reduces when the 2nd, adding 150mg/kg weight (high dose) and 75mg/kg weight (middle dosage) copper citrate
The weightening of full period female sd inbred rats, leukocyte count, content of hemoglobin and male SD rat leukocyte count, significantly reduce female
Property SD Rat Erythrocytes numbers (P<0.05).
The result shows that SD rats without subacute toxicity during copper citrate≤37.5mg/kg body weight doses.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of manufacturing method of feed copper citrate, which is characterized in that comprise the following steps:
(1) sodium citrate and copper sulphate are put into respectively in respective head tank, while adds in isometric soft water, and open steam
Valve dissolves by heating;
(2) open reaction kettle, open simultaneously sodium citrate and copper-bath valve switch, it is lasting to stir, make sodium citrate with
Copper sulphate fully reacts in a kettle;
(3) substance of generation is placed in container and be cooled to room temperature, carry out separating and filtering and be washed with water, filter cake is dried, taken off
Absorption water and partially crystallizable water is gone to can obtain feed copper citrate.
A kind of 2. manufacturing method of feed copper citrate according to claim 1, which is characterized in that the copper sulphate
Mass ratio with sodium citrate is 1:1~1:3.
A kind of 3. manufacturing method of feed copper citrate according to claim 2, which is characterized in that the copper sulphate
Mass ratio with sodium citrate is 1:2.
A kind of 4. manufacturing method of feed copper citrate according to claim 1, which is characterized in that the step
(1) heating for dissolving condition is to be carried out at 80 DEG C in.
A kind of 5. manufacturing method of feed copper citrate according to claim 1, which is characterized in that the step
(2) persistently stirring needs to carry out under 80 DEG C of constant temperature in.
A kind of 6. manufacturing method of feed copper citrate according to claim 1, which is characterized in that the step
(3) drying specific location dries 1h under the conditions of 100 DEG C in.
7. application of the copper citrate that claim 1 preparation method obtains in livestock-raising feed is prepared.
8. application of the copper citrate that claim 1 preparation method obtains in livestock-raising, which is characterized in that by according to body
The premix containing copper citrate is added when focusing on nursing to realize, is added in right amount according to the growth of animal time when feeding,
It is no more than 37.5mg/kg weight under normal circumstances.
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CN201810023685.XA CN108084018A (en) | 2018-01-10 | 2018-01-10 | A kind of manufacturing method of feed copper citrate and its application |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB827523A (en) * | 1957-03-27 | 1960-02-03 | Director Of Technical Services | New organic copper compounds and solutions and mixtures containing the same, and processes for the preparation of such compounds |
CN104892394A (en) * | 2014-10-16 | 2015-09-09 | 郑州瑞普生物工程有限公司 | Preparation method of ammonia copper citrate |
CN106472832A (en) * | 2016-09-28 | 2017-03-08 | 四川省畜科饲料有限公司 | A kind of piglet microelement pre-mix material containing copper citrate and its application |
CN107048041A (en) * | 2017-06-14 | 2017-08-18 | 四川省畜牧科学研究院 | A kind of grower pigs microelement pre-mix material containing copper citrate and preparation method and application |
-
2018
- 2018-01-10 CN CN201810023685.XA patent/CN108084018A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB827523A (en) * | 1957-03-27 | 1960-02-03 | Director Of Technical Services | New organic copper compounds and solutions and mixtures containing the same, and processes for the preparation of such compounds |
CN104892394A (en) * | 2014-10-16 | 2015-09-09 | 郑州瑞普生物工程有限公司 | Preparation method of ammonia copper citrate |
CN106472832A (en) * | 2016-09-28 | 2017-03-08 | 四川省畜科饲料有限公司 | A kind of piglet microelement pre-mix material containing copper citrate and its application |
CN107048041A (en) * | 2017-06-14 | 2017-08-18 | 四川省畜牧科学研究院 | A kind of grower pigs microelement pre-mix material containing copper citrate and preparation method and application |
Non-Patent Citations (2)
Title |
---|
晏家友 等: "不同铜源在畜禽养殖生产中的研究与应用", 《中国畜牧兽医》 * |
金其荣 等: "《有机酸发酵工艺学》", 30 June 1989, 轻工业出版社 * |
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