CN114804215A - Method for producing battery-grade ferrous chloride from cold rolled steel pickling waste acid - Google Patents
Method for producing battery-grade ferrous chloride from cold rolled steel pickling waste acid Download PDFInfo
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- CN114804215A CN114804215A CN202210656488.8A CN202210656488A CN114804215A CN 114804215 A CN114804215 A CN 114804215A CN 202210656488 A CN202210656488 A CN 202210656488A CN 114804215 A CN114804215 A CN 114804215A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
Abstract
The invention discloses a method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid; the method comprises the following steps: heating cold-rolled steel pickling waste acid to 70-98 ℃, then feeding the cold-rolled steel pickling waste acid into a container filled with scrap iron, and collecting reaction liquid passing through the container; adjusting the pH value of the reaction liquid to 3.5-5.5, adding a sulfur-containing compound at the temperature of 70-98 ℃, and keeping the temperature for 0.5-10 min; cooling the obtained reaction liquid, adding a flocculating agent into the reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride, wherein the components in the supernatant meet the requirement of Fe 2+ The concentration is 1.8-3.5 mol/L, Cu 2+ Concentration < 10ppm, Cr 2+ The concentration is less than 10 ppm; the method is environment-friendly and safe, has low energy consumption, and can produce the battery-grade ferrous chloride which completely meets the requirements of downstream enterprises.
Description
Technical Field
The invention belongs to the technical field of steel pickling waste acid treatment, and particularly relates to a method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid.
Background
The continuous pickling production line for cold rolled steel produces large amount of waste acid along with the production of large units, the amount of waste acid produced per hour can reach 20 cubic meters, and the amount of waste acid produced per day can reach nearly 500 cubic meters. Combustion processes are commonly used in the industry to treat the spent acid for conversion to iron oxide, but such processes are energy intensive and have high C emissions, which are environmentally undesirable.
With the market share of new energy automobiles becoming larger and larger, the demand of lithium ion batteries also becomes higher and higher, and the lithium iron phosphate battery becomes a mainstream lithium battery due to the characteristics of nonflammability, good safety performance and the like. One important raw material for producing lithium iron phosphate batteries is battery-grade iron phosphate, and one of the preparation routes is a method for preparing battery-grade iron phosphate by multi-stage reaction disclosed in CN107285292A, namely, the battery-grade iron phosphate is generated by reacting ferric chloride with a phosphorus salt. And reacting the battery-grade iron phosphate with lithium carbonate to prepare the lithium iron phosphate. The lithium iron phosphate electrode material prepared by the method has high demand on raw materials, and the commercially available ferric chloride finished product has high price and low purity, and the content of chromium and copper impurities is more than 20ppm, so that the service life of the battery is influenced.
However, the prior art does not disclose how to produce the raw material meeting the requirement of the lithium iron phosphate electrode material by using the waste acid solution generated after the cold rolled steel is continuously pickled by adopting an environment-friendly method.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid; the waste acid liquid generated after the cold rolled steel is continuously pickled is converted into battery-grade ferrous chloride with the chromium and copper contents less than 10ppm by an environment-friendly method, and further the battery-grade ferrous chloride can be oxidized into battery-grade ferric chloride to be used as a raw material for producing the lithium iron phosphate electrode, so that the industrial utilization value of the waste acid is greatly improved, and the service life of the lithium iron phosphate battery can be remarkably prolonged.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid comprises the following steps:
(1) heating cold-rolled steel pickling waste acid to 70-98 ℃, then feeding the cold-rolled steel pickling waste acid into a container filled with scrap iron, and collecting reaction liquid passing through the container;
(2) adjusting the pH value of the reaction liquid to 3.5-5.5, adding a sulfur-containing compound at the temperature of 70-98 ℃, and keeping the temperature for 0.5-10 min;
(3) and (3) cooling the reaction liquid obtained in the step (2), adding a flocculating agent into the reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride.
The cold rolled steel is preferably plain carbon steel.
In the step (1), the iron content and the hydrogen chloride content in the cold-rolled steel pickling waste acid are respectively 50-135 g/L and 10-60 g/L.
In the step (1), the time for the heated waste acid to pass through a container filled with scrap iron is 5-25 hours.
In the step (1), the content of free HCl in the reaction liquid passing through the container is 0.03-5 g/L, and the content of iron is 80-190 g/L.
In the step (2), alkaline salt is used for adjusting the pH value of the reaction liquid passing through the container to 3.5-5.5.
The alkaline salt is any one or more of sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
In the step (2), the sulfur-containing compound is any one or more of potassium thioacetate, thioacetamide and thiourea; the solid-liquid ratio of the sulfur-containing compound to the reaction liquid is 1 g: 500-15000 mL.
In the step (3), when the flocculating agent is added, the temperature of the reaction liquid is controlled to be 35-55 ℃.
In the step (3), the flocculating agent is polyacrylamide.
In the step (3), the amount of the flocculant added in each liter of reaction liquid is 0.1-0.2 g.
In the step (3), if Fe in the supernatant is contained 2+ Less than 1.8mol/L, and vacuum evaporating the supernatant to obtain Fe 2+ The concentration is 1.8-3.5 mol/L.
The invention also provides battery grade ferrous chloride produced by the method, and Fe in the battery grade ferrous chloride 2+ The concentration is 1.8-3.5 mol/L, Cu 2+ Concentration < 10ppm, Cr 2+ The concentration is less than 10ppm, and the battery grade ferrous chloride can be directly supplied to downstream companies for preparing the iron phosphate and further preparing the battery grade lithium iron phosphate electrode material.
The method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid comprises the steps of heating cold-rolled steel pickling waste acid with iron content of 50-135 g/L and hydrogen chloride content of 10-60 g/L to 70-98 ℃, feeding the cold-rolled steel pickling waste acid into a container filled with scrap iron, reacting the waste acid with the scrap iron in the container, wherein free HCl content in reaction liquid after reaction is 0.03-5 g/L, and iron content is 80-190 g/L; and then adjusting the pH value of the reaction liquid to 3.5-5.5, adding a sulfur-containing compound at the temperature of 70-98 ℃, and keeping the temperature for 0.5-10 min, wherein in the process, if the used sulfur-containing compound is potassium thioacetate, thioacetamide or thiourea, in a hot ferrous chloride solution, the sulfide reacts as follows:
C 2 H 3 KOS+H 2 O＝CH 3 COOK+H 2 s, hydrogen sulfide generated by reaction and copper ions, chromium ions, lead ions and the like easily form sulfide precipitates, and a ferrous chloride solution is purified;
CH 3 CSNH 2 +H 2 O＝CH 3 CONH 2 +H 2 s, hydrogen sulfide generated by reaction and copper ions, chromium ions, lead ions and the like easily form sulfide precipitates, and a ferrous chloride solution is purified;
CS(NH 2 ) 2 +2H 2 O＝CO 2 +2NH 3 +H 2 s; the ammonia generated by the reaction can improve the pH value of the reaction liquid, the hydrogen sulfide, copper ions, chromium ions, lead ions and the like can easily form sulfide precipitates, the ferrous chloride solution is purified, the carbon dioxide plays a role in stirring to enable the solution to be uniform, and other elements are not introduced in the process to pollute the solution.
Then adding flocculating agent to the reaction liquid after cooling to remove the copper, chromium and other metal sulfide precipitate, obtaining supernatant fluid which is battery-grade ferrous chloride, wherein Fe in the supernatant fluid 2+ The concentration is 1.8-3.5 mol/L, Cu 2+ Concentration < 10ppm, Cr 2 + The concentration is less than 10ppm, and the index can completely meet the requirements of downstream enterprises.
Compared with the prior art, the invention has the following beneficial effects:
1. the method provided by the invention can produce the battery-grade ferrous chloride from the cold-rolled steel pickling waste acid, thereby realizing the reutilization of resources;
2. according to the invention, the solid sulfur-containing compound which is not easy to volatilize is adopted to complete the precipitation of impurities in the waste acid after the reaction with the scrap iron and reduce the introduction of other elements, and the added sulfur-containing compound forms hydrogen sulfide in the solution to purify the reaction solution, so that the addition is convenient and safe;
3. in the present invention, before adding the solid sulfur-containing compound, it is preferable to adjust the pH of the reaction solution using any one or more of sodium carbonate, sodium bicarbonate, and ammonium bicarbonate, which generate CO by heating after being added to the reaction solution 2 Gas, which can make the solution react more uniformly under the stirring action;
4. adding a sulfur-containing compound at the temperature of 70-98 ℃, and reacting quickly and uniformly after adding;
5. fe in ferrous chloride solution produced according to the method of the invention 2+ The concentration is 1.8-3.5 mol/L, Cu 2+ Concentration < 10ppm, Cr 2+ The concentration is less than 10ppm, the index can completely meet the requirements of downstream enterprises, and the downstream enterprises require to control Fe 2+ Cu with a concentration of 1.8mol/L or more 2+ Concentration < 10ppm, Cr 2+ The concentration is less than 10 ppm.
Detailed Description
The present invention will be described in detail with reference to examples.
The waste acid in each example is the waste acid obtained after pickling the cold-rolled steel strip made of plain carbon steel, and the content of iron in the waste acid is 115g/L, the content of hydrogen chloride is 50g/L, the content of copper ions is 34ppm, and the content of chromium ions is 26 ppm.
Example 1
A method for producing battery-grade ferrous chloride from cold rolled steel pickling waste acid is characterized by comprising the following steps:
(1) heating waste acid to 85 ℃, then sending the waste acid into a container filled with scrap iron to react with the scrap iron for 15 hours, and collecting reaction liquid passing through the container, wherein the content of iron in the reaction liquid is 150g/L, and the content of hydrogen chloride in the reaction liquid is 5 g/L;
(2) adding ammonium bicarbonate without stirring, and stirring the generated carbon dioxide gas to ensure that the pH value of the solution is 3.5; adding 114mg of potassium thioacetate into each liter of reaction solution, and keeping the temperature for 8 min;
(3) and (3) cooling the reaction liquid obtained in the step (2) to 35 ℃, then adding 0.1g of polyacrylamide into each liter of reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride solution.
Example 2
A method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid is characterized by comprising the following steps:
(1) heating waste acid to 85 ℃, then sending the waste acid into a container filled with scrap iron to react with the scrap iron for 15 hours, and collecting reaction liquid passing through the container, wherein the content of iron in the reaction liquid is 150g/L, and the content of hydrogen chloride in the reaction liquid is 5 g/L;
(2) adding ammonium bicarbonate without stirring, and stirring the generated carbon dioxide gas to ensure that the pH value of the solution is 4.0; adding 1.14g of potassium thioacetate into each liter of reaction solution, and keeping the temperature for 7 min;
(3) and (3) cooling the reaction liquid obtained in the step (2) to 40 ℃, then adding 0.15g of polyacrylamide into each liter of reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride solution.
Example 3
A method for producing battery-grade ferrous chloride from cold rolled steel pickling waste acid is characterized by comprising the following steps:
(1) heating waste acid to 85 ℃, then sending the waste acid into a container filled with scrap iron to react with the scrap iron for 15 hours, and collecting reaction liquid passing through the container, wherein the content of iron in the reaction liquid is 150g/L, and the content of hydrogen chloride in the reaction liquid is 5 g/L;
(2) adding ammonium bicarbonate without stirring, and stirring the generated carbon dioxide gas to ensure that the pH value of the solution is 4.5; adding thioacetamide 40mg into each liter of reaction solution, and keeping the temperature for 7 min;
(3) and (3) cooling the reaction liquid obtained in the step (2) to 40 ℃, then adding 0.1g of polyacrylamide into each liter of reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride solution.
Example 4
A method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid is characterized by comprising the following steps:
(1) heating waste acid to 85 ℃, then sending the waste acid into a container filled with scrap iron to react with the scrap iron for 15 hours, and collecting reaction liquid passing through the container, wherein the content of iron in the reaction liquid is 150g/L, and the content of hydrogen chloride in the reaction liquid is 5 g/L;
(2) adding ammonium bicarbonate without stirring, and stirring the generated carbon dioxide gas to ensure that the pH value of the solution is 3.5; adding 120mg of thiourea into each liter of reaction solution, and keeping the temperature for 5 min;
(3) and (3) cooling the reaction liquid obtained in the step (2) to 35 ℃, then adding 0.1g of polyacrylamide into each liter of reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride solution.
The contents of the respective substances in the battery grade ferrous chloride solution prepared in each example are shown in table 1:
TABLE 1 test data for battery grade ferrous chloride solutions obtained in each example
The above detailed description of a process for producing battery grade ferrous chloride from cold rolled steel pickling waste acid, with reference to the examples, is illustrative and not restrictive, and several examples are set forth within the scope of the invention, thus variations and modifications that do not depart from the general concept of the invention are intended to be within the scope of the invention.
Claims (10)
1. A method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid is characterized by comprising the following steps:
(1) heating cold-rolled steel pickling waste acid to 70-98 ℃, then feeding the cold-rolled steel pickling waste acid into a container filled with scrap iron, and collecting reaction liquid passing through the container;
(2) adjusting the pH value of the reaction liquid to 3.5-5.5, adding a sulfur-containing compound at the temperature of 70-98 ℃, and keeping the temperature for 0.5-10 min;
(3) and (3) cooling the reaction liquid obtained in the step (2), adding a flocculating agent into the reaction liquid, standing for precipitation, and filtering to obtain supernatant, namely the battery-grade ferrous chloride.
2. The method according to claim 1, wherein in the step (1), the iron content of the cold-rolled steel pickling waste acid is 50-135 g/L, and the hydrogen chloride content is 10-60 g/L.
3. The method according to claim 1, wherein in the step (1), the heated waste acid passes through the container filled with the iron pieces for 5 to 25 hours.
4. The method according to claim 1, wherein in the step (1), the reaction solution passing through the vessel has a free HCl content of 0.03 to 5g/L and an iron content of 80 to 190 g/L.
5. The method according to claim 1, wherein in the step (2), the pH of the reaction solution passing through the vessel is adjusted to 3.5 to 5.5 using an alkaline salt.
6. The method according to claim 5, wherein the basic salt is any one or more of sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
7. The method according to claim 1, wherein in the step (2), the sulfur-containing compound is any one or more of potassium thioacetate, thioacetamide and thiourea; the solid-liquid ratio of the sulfur-containing compound to the reaction liquid is 1 g: 500-15000 mL.
8. The method according to claim 1, characterized in that in the step (3), when the flocculating agent is added, the temperature of the reaction liquid is controlled to be 35-55 ℃; the amount of the flocculant added in each liter of reaction liquid is 0.1-0.2 g.
9. The method according to claim 1, wherein in step (3), if Fe is in the supernatant 2+ Less than 1.8mol/L, and vacuum evaporating the supernatant to obtain Fe 2+ The concentration is 1.8-3.5 mol/L.
10. Battery grade ferrous chloride produced by the method of any one of claims 1 to 9.
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| WO2011147426A1 (en) * | 2010-05-24 | 2011-12-01 | Mohammed Mohammed Mohammed Saad | A process of production of concentrated ferric chloride solution from the waste hydrochloric acid pickle liquor |
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