CN107903166A - A kind of preparation method of feed grade copper citrate - Google Patents
A kind of preparation method of feed grade copper citrate Download PDFInfo
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- CN107903166A CN107903166A CN201711115817.3A CN201711115817A CN107903166A CN 107903166 A CN107903166 A CN 107903166A CN 201711115817 A CN201711115817 A CN 201711115817A CN 107903166 A CN107903166 A CN 107903166A
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- copper citrate
- copper
- citric acid
- feed grade
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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
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of feed grade copper citrate, comprises the following steps：(1) by citric acid and water input reaction kettle, 20%~25% aqueous citric acid solution is formed, and be heated to 80 DEG C~100 DEG C；(2) turn on agitator, according to citric acid and basic copper carbonate 1:The mass ratio of (0.8~1), is slowly added to basic copper carbonate and carries out neutralization reaction, generate copper citrate, and it is 4~6 to add a little citric acid to control reacting solution pH value, the CO of generation2Gas enters absorption groove by exhaust outlet and is absorbed；(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtains copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；(4) obtained copper citrate crystal is put into drier 1~2h of drying under the conditions of 100 DEG C~120 DEG C, sloughs partially crystallizable water, you can feed grade copper citrate finished product is made.The product yield rate of the method for the present invention is high, and impurity is few, and production process is environmentally protective.
Description
Technical field
The invention belongs to feed additive field, and in particular to a kind of preparation method of feed grade copper citrate.
Background technology
In recent years, internal feed and breeding enterprise application new copper source mainly have amino acid network (chela) close copper, copper proteinate,
Yeast copper, basic copper chloride etc., wherein amino acid network (chela) close copper, copper proteinate, yeast copper belong to organic copper, and basic copper chloride
For Inorganic Copper.Most of result of study all confirms that the biology utilization rate of organic copper is higher than Inorganic Copper, and can reduce animal
Excrement copper content in excreta, reduces pollution of the heavy metal to environment.But existing amino acid network (chela) closes copper, copper proteinate, ferment
Existing main problem is a lack of the straightway testing evidence of chemical characteristic or mechanism of action to female copper in practical applications, it is difficult to explain
The inconsistent phenomenon of result of the test；In addition price factor also limit its further genralrlization as high efficiency animal copper source.
Organic acid organic trace element have active constituent content is high, product stability is good, method of quality control is ripe,
The relatively low advantage of production cost.There is research to think, citric acid can be used as ligand, and chelation occurs with mineral matter.At 25 DEG C
When, the complexation constant (Igk) of citric acid and copper ion is 14.2, thus citric acid can be formed with copper ion it is stable, biological
The higher complex of potency is learned, so as to promote absorption of the animal intestinal tract to mineral element.
At present, the related introduction of feed grade copper citrate production technology is not yet found.On food pharmaceutical grade copper citrate,
Common production method is that copper citrate is made for raw material and edible citric acid reaction using copper carbonate and cupric oxide, but this
Method is not suitable for producing feed grade copper citrate, because copper carbonate is insoluble in water, is not reacted with water, can not obtain pure carbon
Sour copper, can be only formed mixture, and cupric oxide belongs to noxious material, may be to direct labor if making raw material with cupric oxide
Health care belt carrys out high risks, wrongly take or suck a large amount of cupric oxide dust occur shiver, body temperature rise, while pierced with respiratory tract
Swash symptom, Long Term Contact, may cause respiratory tract and eye conjunctiva stimulation, nosebleed epistaxis, schneiderian membrane blutpunkte or ulcer, or even nasal septum
Perforation 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 preparation side of feed grade copper citrate
Method, product yield rate is high, and impurity is few, and production process is environmentally protective.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of feed grade copper citrate, comprises the following steps：
Step 1：By in citric acid and water input reaction kettle, 20%~25% aqueous citric acid solution is formed, and be heated to
80 DEG C~100 DEG C；
Step 2：Turn on agitator, according to citric acid and basic copper carbonate 1:The mass ratio of (0.8~1), is slowly added to alkali
Formula copper carbonate carries out neutralization reaction, generates copper citrate, and it is 4~6 to add a little citric acid to control reacting solution pH value, is produced
CO2Gas enters absorption groove by exhaust outlet and is absorbed；
Step 3：By the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated,
Copper citrate crystal is obtained, and separation waste liquid is discharged into waste liquid pool and is recycled；
Step 4：By obtained copper citrate crystal be put into drier under the conditions of 100 DEG C~120 DEG C drying 1~
2h, sloughs partially crystallizable water, you can feed grade copper citrate finished product is made.
Further, the citric acid is food grade materials, and basic copper carbonate is feed grade raw material.
Further, the water that step 1 uses is mixed by the separation waste liquid of deionized water and step 3.
Further, the absorbing liquid in the absorption groove is NaOH or Ca (OH)2Solution.
The beneficial effects of the present invention are：
(1) unused virose cupric oxide, the actual bodily harm caused by without to operating personnel, under sour environment,
I.e. excessive citric acid can cause basic copper carbonate to react completely, and then carry out filtration treatment again so that product net content
Reach top, avoiding the problem that conventional production process, there are the impurity such as copper carbonate.
(2) feed grade copper citrate, whole production are prepared using food-grade citric acid and the reaction of feed grade basic copper carbonate
Process green, environmental protection, nonhazardous, pollution are small.
(3) accessory substance in feed grade copper citrate production process is CO2And H2O。CO2It is drained into through exhaust outlet equipped with alkali
Property solution such as NaOH or Ca (OH)2Absorption groove in, available for sodium bicarbonate, detergent or construction material is prepared, be easily handled；Point
Circulation can be used for produce from waste liquid, cost can simultaneously be reduced by reducing discharging of waste liquid.
Brief description of the drawings
Attached drawing 1 is process flow chart of the invention.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
A kind of preparation method of feed grade copper citrate, comprises the following steps：
(1) it is the citric acid in 100kg citric acids and 400kg deionized waters metering input reaction kettle, forming 20% is water-soluble
Liquid, and it is heated to 80 DEG C；
(2) turn on agitator, is slowly added to 100kg basic copper carbonates and carries out neutralization reaction, generate copper citrate, utilize lemon
It is 4 that lemon acid, which controls reacting solution pH value, the CO of generation2Gas is inhaled by exhaust outlet into the absorption groove for filling NaOH solution
Receive；
(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
(4) obtained copper citrate crystal is put into drier and dries 1h under the conditions of 100 DEG C, slough partially crystallizable
Water, is made 150.8kg copper citrate finished products.
Feed grade copper citrate quality index：Copper citrate content 99.65%, copper content 35.16%, citrate content
54.13%, loss on drying 6.20%, arsenic content 0.0002%, lead content 0.0008%.
Embodiment 2
A kind of preparation method of feed grade copper citrate, comprises the following steps：
(1) by 100kg citric acids and 300kg water (deionized water and the mixed liquor for separating waste liquid) metering input reaction kettle
In, 25% aqueous citric acid solution is formed, and be heated to 100 DEG C；
(2) turn on agitator, is slowly added to 100kg basic copper carbonates and carries out neutralization reaction, generates copper citrate, and control is anti-
It is 6 to answer solution ph, the CO of generation2Gas is absorbed by exhaust outlet into the absorption groove for filling NaOH solution；
(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
(4) obtained copper citrate crystal is put into drier and dries 2h under the conditions of 120 DEG C, slough partially crystallizable
Water, is made 152.4kg copper citrate finished products.
Feed grade copper citrate quality index：Copper citrate content 99.96%, copper content 35.27%, citrate content
55.10%, loss on drying 8.30%, arsenic content 0.0002%, lead content 0.0006%.
Embodiment 3
A kind of preparation method of feed grade copper citrate, comprises the following steps：
(1) by 100kg citric acids and 376kg water (deionized water and the mixed liquor for separating waste liquid) metering input reaction kettle
In, 21% aqueous citric acid solution is formed, and be heated to 90 DEG C；
(2) turn on agitator, is slowly added to 90kg basic copper carbonates and carries out neutralization reaction, generates copper citrate, and control is anti-
It is 5 to answer solution ph, the CO of generation2Gas is entered by exhaust outlet fills Ca (OH)2The absorption groove of solution is absorbed；
(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
(4) obtained copper citrate crystal is put into drier and dries 1.5h under the conditions of 110 DEG C, slough partially crystallizable
Water, is made 154.0kg copper citrate finished products.
Feed grade copper citrate quality index：Copper citrate content 99.84%, copper content 35.18%, citrate content
56.18%, loss on drying 9.00%, arsenic content 0.0002%, lead content 0.0005%.
Embodiment 4
A kind of preparation method of feed grade copper citrate, comprises the following steps：
(1) by 100kg citric acids and 335kg water (deionized water and the mixed liquor for separating waste liquid) metering input reaction kettle
In, 23% aqueous citric acid solution is formed, and be heated to 90 DEG C；
(2) turn on agitator, is slowly added to 100kg basic copper carbonates and carries out neutralization reaction, generates copper citrate, and control is anti-
It is 4.5 to answer solution ph, the CO of generation2Gas is absorbed by exhaust outlet into the absorption groove for filling NaOH solution；
(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
(4) obtained copper citrate crystal is put into drier and dries 1.6h under the conditions of 105 DEG C, slough partially crystallizable
Water, is made 152.2kg copper citrate finished products.
Feed grade copper citrate quality index：Copper citrate content 98.00%, copper content 34.55%, citrate content
51.89%, loss on drying 9.40%, arsenic content 0.0002%, lead content 0.0007%.
Embodiment 5
A kind of preparation method of feed grade copper citrate, comprises the following steps：
(1) by 100kg citric acids and 355kg water (deionized water and the mixed liquor for separating waste liquid) metering input reaction kettle
In, 22% aqueous citric acid solution is formed, and be heated to 95 DEG C；
(2) turn on agitator, is slowly added to 100kg basic copper carbonates and carries out neutralization reaction, generates copper citrate, and control is anti-
It is 5.5 to answer solution ph, the CO of generation2Gas is absorbed by exhaust outlet into the absorption groove for filling NaOH solution；
(3) by the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
(4) obtained copper citrate crystal is put into drier and dries 1.8h under the conditions of 115 DEG C, slough partially crystallizable
Water, is made 154.3kg copper citrate finished products.
Feed grade copper citrate quality index：Copper citrate content 98.00%, copper content 34.58%, citrate content
51.15%, loss on drying 9.60%, arsenic content 0.0002%, lead content 0.0003%.
The feed grade copper citrate prepared using the method for the present invention can be seen that by each embodiment, content is up to
More than 98%, 99.96% is reached as high as, impurity is considerably less, and other content of beary metal are almost close to zero.
Claims (4)
1. a kind of preparation method of feed grade copper citrate, it is characterised in that comprise the following steps：
Step 1：By in citric acid and water input reaction kettle, 20%~25% aqueous citric acid solution is formed, and be heated to 80 DEG C
~100 DEG C；
Step 2：Turn on agitator, according to citric acid and basic copper carbonate 1:The mass ratio of (0.8~1), is slowly added to alkali formula carbon
Sour copper carries out neutralization reaction, generates copper citrate, and it is 4~6 to add a little citric acid to control reacting solution pH value, generation
CO2Gas enters absorption groove by exhaust outlet and is absorbed；
Step 3：By the copper citrate of generation after filtering, concentrate, be cooled to room temperature, it is put into centrifuge and is dehydrated, obtained
Copper citrate crystal, and separation waste liquid is discharged into waste liquid pool and is recycled；
Step 4：Obtained copper citrate crystal is put into drier 1~2h of drying under the conditions of 100 DEG C~120 DEG C, is sloughed
Partially crystallizable water, you can feed grade copper citrate finished product is made.
2. the preparation method of feed grade copper citrate as claimed in claim 1, it is characterised in that the citric acid is food-grade
Raw material, basic copper carbonate are feed grade raw material.
3. the preparation method of feed grade copper citrate as claimed in claim 1, it is characterised in that the water that step 1 uses is by going
Ionized water and the separation waste liquid of step 3 mix.
4. the preparation method of feed grade copper citrate as claimed in claim 1, it is characterised in that the suction in the absorption groove
Receipts liquid is NaOH or Ca (OH)2Solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711115817.3A CN107903166B (en) | 2017-11-13 | 2017-11-13 | Preparation method of feed-grade copper citrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711115817.3A CN107903166B (en) | 2017-11-13 | 2017-11-13 | Preparation method of feed-grade copper citrate |
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| CN107903166A true CN107903166A (en) | 2018-04-13 |
| CN107903166B CN107903166B (en) | 2021-07-06 |
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| CN201711115817.3A Active CN107903166B (en) | 2017-11-13 | 2017-11-13 | Preparation method of feed-grade copper citrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357778A (en) * | 2019-08-02 | 2019-10-22 | 湖南柿竹园有色金属有限责任公司 | A kind of preparation method of bismuth citrate |
| CN111777502A (en) * | 2020-06-15 | 2020-10-16 | 四川吉隆达生物科技集团有限公司 | Preparation method of high-purity citric acid chelated copper |
Citations (3)
| 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 |
| CN104557518A (en) * | 2014-12-22 | 2015-04-29 | 南通市飞宇精细化学品有限公司 | Production process of cupric citrate |
| CN106316834A (en) * | 2015-06-23 | 2017-01-11 | 天津市光复科技发展有限公司 | Coproduction method of crystallized cupric acetate and anhydrous cupric acetate |
-
2017
- 2017-11-13 CN CN201711115817.3A patent/CN107903166B/en active Active
Patent Citations (3)
| 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 |
| CN104557518A (en) * | 2014-12-22 | 2015-04-29 | 南通市飞宇精细化学品有限公司 | Production process of cupric citrate |
| CN106316834A (en) * | 2015-06-23 | 2017-01-11 | 天津市光复科技发展有限公司 | Coproduction method of crystallized cupric acetate and anhydrous cupric acetate |
Non-Patent Citations (1)
| Title |
|---|
| 龚玉琼等: "饲料添加剂―柠檬酸铜螯合物的微波固相合成", 《中国饲料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357778A (en) * | 2019-08-02 | 2019-10-22 | 湖南柿竹园有色金属有限责任公司 | A kind of preparation method of bismuth citrate |
| CN110357778B (en) * | 2019-08-02 | 2022-02-11 | 湖南柿竹园有色金属有限责任公司 | Preparation method of bismuth citrate |
| CN111777502A (en) * | 2020-06-15 | 2020-10-16 | 四川吉隆达生物科技集团有限公司 | Preparation method of high-purity citric acid chelated copper |
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| CN107903166B (en) | 2021-07-06 |
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