CN107903166B - Preparation method of feed-grade copper citrate - Google Patents
Preparation method of feed-grade copper citrate Download PDFInfo
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- CN107903166B CN107903166B CN201711115817.3A CN201711115817A CN107903166B CN 107903166 B CN107903166 B CN 107903166B CN 201711115817 A CN201711115817 A CN 201711115817A CN 107903166 B CN107903166 B CN 107903166B
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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
Abstract
A preparation method of feed-grade copper citrate comprises the following steps: (1) adding citric acid and water into a reaction kettle to form 20-25% citric acid aqueous solution, and heating to 80-100 ℃; (2) starting a stirrer, slowly adding basic copper carbonate according to the mass ratio of citric acid to basic copper carbonate 1 (0.8-1) to perform a neutralization reaction to generate copper citrate, adding a little citric acid to control the pH value of a reaction solution to be 4-6, and generating CO2The gas enters the absorption tank through the exhaust port to be absorbed; (3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling; (4) and (3) putting the obtained copper citrate crystal into a dryer, drying for 1-2 h at the temperature of 100-120 ℃, and removing part of crystal water to obtain the feed-grade copper citrate finished product. The method has the advantages of high product yield, less impurities and green and environment-friendly production process.
Description
Technical Field
The invention belongs to the field of feed additives, and particularly relates to a preparation method of feed-grade copper citrate.
Background
In recent years, the novel copper sources applied to domestic feed and breeding enterprises mainly comprise amino acid copper complex (chelate), protein copper, yeast copper, basic copper chloride and the like, wherein the amino acid copper complex (chelate), the protein copper and the yeast copper belong to organic copper, and the basic copper chloride is inorganic copper. Most research results prove that the biological utilization rate of the organic copper is higher than that of the inorganic copper, the content of the fecal copper in animal excrement can be reduced, and the pollution of heavy metal to the environment can be reduced. However, the main problems of the existing amino acid complex (chelated) copper, protein copper and yeast copper in practical application are that direct test evidence of chemical characteristics or action mechanisms is lacked, and the phenomenon that test results are inconsistent is difficult to explain; in addition, the further popularization of the copper source as an animal high-efficiency copper source is limited by price factors.
The organic acid organic trace elements have the advantages of high content of effective components, good product stability, mature quality control method and lower production cost. It is believed that citric acid acts as a ligand to chelate minerals. At 25 ℃, the complexation constant (Igk) of citric acid and copper ions is 14.2, so that the citric acid and the copper ions can form a stable coordination compound with higher biological value, thereby promoting the absorption of mineral elements by animal intestinal tracts.
At present, the related introduction of the production process of feed-grade copper citrate is not found. Regarding food and medicine grade copper citrate, the common production method is to utilize copper carbonate and copper oxide as raw materials to react with edible citric acid to prepare the copper citrate, but the method is not suitable for producing feed grade copper citrate, because the copper carbonate is insoluble in water and does not react with water, pure copper carbonate cannot be obtained, only a mixture can be formed, the copper oxide belongs to toxic substances, if the copper oxide is used as the raw material, great harm can be brought to the health of production workers, cold tremor and body temperature rise can be caused by taking or inhaling a large amount of copper oxide dust by mistake, respiratory tract irritation symptoms are accompanied, and respiratory tract irritation, eye conjunctiva irritation, epistaxis, nasal mucosa bleeding points or ulcers, even perforation of nasal septum and dermatitis can be caused by long-term contact.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the feed-grade copper citrate, which has the advantages of high product yield, less impurities and green and environment-friendly production process.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of feed-grade copper citrate comprises the following steps:
the method comprises the following steps: adding citric acid and water into a reaction kettle to form 20-25% citric acid aqueous solution, and heating to 80-100 ℃;
step two: starting a stirrer, slowly adding basic copper carbonate according to the mass ratio of citric acid to basic copper carbonate 1 (0.8-1) to perform a neutralization reaction to generate copper citrate, and adding a little citric acid to control the pH value of a reaction solutionValue of 4-6, CO produced2The gas enters the absorption tank through the exhaust port to be absorbed;
step three: filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
step four: and (3) putting the obtained copper citrate crystal into a dryer, drying for 1-2 h at the temperature of 100-120 ℃, and removing part of crystal water to obtain the feed-grade copper citrate finished product.
Further, the citric acid is a food-grade raw material, and the basic copper carbonate is a feed-grade raw material.
Further, the water used in the first step is formed by mixing deionized water and the separated waste liquid in the third step.
Further, the absorption liquid in the absorption tank is NaOH or Ca (OH)2And (3) solution.
The invention has the beneficial effects that:
(1) the method has the advantages that toxic copper oxide is not used, so that physical injury to operators can be avoided, in an acidic environment, namely, the excessive citric acid can enable basic copper carbonate to completely react, and then filtration treatment is carried out, so that the net content of a product reaches the highest degree, and the problem of impurities such as copper carbonate existing in a conventional production method is avoided.
(2) The feed-grade copper citrate is prepared by reacting food-grade citric acid with feed-grade basic copper carbonate, and the whole production process is green, environment-friendly, non-toxic and low in pollution.
(3) The byproduct in the production process of feed-grade copper citrate is CO2And H2O。CO2Discharging through an exhaust port to a container containing an alkaline solution such as NaOH or Ca (OH)2The absorption tank can be used for preparing baking soda, detergent or building materials, and is easy to process; the separated waste liquid can be used for circular production, thereby reducing the discharge of the waste liquid and reducing the cost.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of feed-grade copper citrate comprises the following steps:
(1) metering 100kg of citric acid and 400kg of deionized water into a reaction kettle to form a 20% citric acid aqueous solution, and heating to 80 ℃;
(2) starting a stirrer, slowly adding 100kg of basic copper carbonate for neutralization reaction to generate copper citrate, controlling the pH value of the reaction solution to be 4 by using citric acid, and generating CO2The gas enters an absorption tank filled with NaOH solution through an exhaust port to be absorbed;
(3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
(4) and (3) putting the obtained copper citrate crystal into a dryer, drying for 1h at the temperature of 100 ℃, and removing part of crystal water to obtain 150.8kg of finished copper citrate product.
The quality indexes of the feed-grade copper citrate are as follows: 99.65% of copper citrate, 35.16% of copper, 54.13% of citrate, 6.20% of drying weight loss, 0.0002% of arsenic and 0.0008% of lead.
Example 2
A preparation method of feed-grade copper citrate comprises the following steps:
(1) 100kg of citric acid and 300kg of water (a mixed solution of deionized water and a separation waste liquid) are metered into a reaction kettle to form a 25% citric acid aqueous solution, and the citric acid aqueous solution is heated to 100 ℃;
(2) starting a stirrer, slowly adding 100kg of basic copper carbonate for neutralization reaction to generate copper citrate, controlling the pH value of the reaction solution to be 6, and generating CO2The gas enters an absorption tank filled with NaOH solution through an exhaust port to be absorbed;
(3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
(4) and (3) putting the obtained copper citrate crystals into a dryer, drying for 2h at the temperature of 120 ℃, and removing part of crystal water to obtain 152.4kg of finished copper citrate products.
The quality indexes of the feed-grade copper citrate are as follows: 99.96% of copper citrate, 35.27% of copper, 55.10% of citrate, 8.30% of drying weight loss, 0.0002% of arsenic and 0.0006% of lead.
Example 3
A preparation method of feed-grade copper citrate comprises the following steps:
(1) 100kg of citric acid and 376kg of water (a mixed solution of deionized water and a separation waste liquid) are metered into a reaction kettle to form a 21% citric acid aqueous solution, and the citric acid aqueous solution is heated to 90 ℃;
(2) starting a stirrer, slowly adding 90kg of basic copper carbonate for neutralization reaction to generate copper citrate, controlling the pH value of the reaction solution to be 5, and generating CO2The gas enters the container with Ca (OH) through the exhaust port2The absorption tank of the solution is absorbed;
(3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
(4) and (3) putting the obtained copper citrate crystal into a dryer, drying for 1.5h at the temperature of 110 ℃, and removing part of crystal water to obtain 154.0kg of finished copper citrate product.
The quality indexes of the feed-grade copper citrate are as follows: 99.84% of copper citrate, 35.18% of copper, 56.18% of citrate, 9.00% of loss on drying, 0.0002% of arsenic and 0.0005% of lead.
Example 4
A preparation method of feed-grade copper citrate comprises the following steps:
(1) 100kg of citric acid and 335kg of water (a mixed solution of deionized water and a separation waste liquid) are metered into a reaction kettle to form a 23% citric acid aqueous solution, and the citric acid aqueous solution is heated to 90 ℃;
(2) starting the stirrer, slowly adding 100kg of basic copper carbonate for neutralization reactionGenerating copper citrate, controlling the pH value of the reaction solution to be 4.5, and generating CO2The gas enters an absorption tank filled with NaOH solution through an exhaust port to be absorbed;
(3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
(4) and (3) putting the obtained copper citrate crystals into a dryer, drying for 1.6h at 105 ℃, and removing part of crystal water to obtain 152.2kg of finished copper citrate products.
The quality indexes of the feed-grade copper citrate are as follows: the copper citrate content is 98.00 percent, the copper content is 34.55 percent, the citrate content is 51.89 percent, the drying weight loss is 9.40 percent, the arsenic content is 0.0002 percent, and the lead content is 0.0007 percent.
Example 5
A preparation method of feed-grade copper citrate comprises the following steps:
(1) 100kg of citric acid and 355kg of water (a mixed solution of deionized water and a separation waste liquid) are metered into a reaction kettle to form a 22% citric acid aqueous solution, and the mixture is heated to 95 ℃;
(2) starting a stirrer, slowly adding 100kg of basic copper carbonate for neutralization reaction to generate copper citrate, controlling the pH value of the reaction solution to be 5.5, and generating CO2The gas enters an absorption tank filled with NaOH solution through an exhaust port to be absorbed;
(3) filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
(4) and putting the obtained copper citrate crystal into a dryer, drying for 1.8h at the temperature of 115 ℃, and removing part of crystal water to obtain 154.3kg of a finished product of the copper citrate.
The quality indexes of the feed-grade copper citrate are as follows: the copper citrate content is 98.00 percent, the copper content is 34.58 percent, the citrate content is 51.15 percent, the drying weight loss is 9.60 percent, the arsenic content is 0.0002 percent, and the lead content is 0.0003 percent.
According to various embodiments, the feed-grade copper citrate prepared by the method has the content of over 98 percent, the highest content of 99.96 percent, very few impurities and almost zero content of other heavy metals.
Claims (1)
1. A preparation method of feed-grade copper citrate is characterized by comprising the following steps:
step (1), 100kg of citric acid and 300kg of water are metered into a reaction kettle to form 25% of citric acid aqueous solution, and the solution is heated to 100%oC；
Step (2), starting a stirrer, slowly adding 100kg of basic copper carbonate for neutralization reaction to generate copper citrate, controlling the pH value of the reaction solution to be 6, and generating CO2The gas enters an absorption tank filled with NaOH solution through an exhaust port to be absorbed;
filtering, concentrating and cooling the generated copper citrate to room temperature, putting the copper citrate into a centrifugal machine for dehydration to obtain copper citrate crystals, and discharging the separated waste liquid into a waste liquid pool for recycling;
step (4), putting the obtained copper citrate crystals into a dryer at 120 DEGoDrying for 2h under the condition of C, and removing part of crystal water to obtain 152.4kg of feed-grade copper citrate finished product;
the water used in the step (1) is formed by mixing deionized water and the separated waste liquid in the step (3); the quality indexes of the feed-grade copper citrate are as follows: 99.96% of copper citrate, 35.27% of copper, 55.10% of citrate, 8.30% of drying weight loss, 0.0002% of arsenic and 0.0006% of lead.
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| 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 |
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 |
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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 |
|---|
| 饲料添加剂―柠檬酸铜螯合物的微波固相合成;龚玉琼等;《中国饲料》;20161231(第08期);第22-24页 * |
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