CN115010185A - Production method of battery-grade ferrous chloride - Google Patents
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- CN115010185A CN115010185A CN202210656186.0A CN202210656186A CN115010185A CN 115010185 A CN115010185 A CN 115010185A CN 202210656186 A CN202210656186 A CN 202210656186A CN 115010185 A CN115010185 A CN 115010185A
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- 229960002089 ferrous chloride Drugs 0.000 title claims abstract description 36
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000002699 waste material Substances 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 19
- 238000005554 pickling Methods 0.000 claims abstract description 17
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006228 supernatant Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008394 flocculating agent Substances 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 159000000011 group IA salts Chemical class 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a production method of battery-grade ferrous chloride; the method comprises the following steps: heating cold-rolled steel pickling waste acid to 80-98 ℃, then feeding the cold-rolled steel pickling waste acid into a container filled with scrap iron, and collecting reaction liquid passing through the container; adding aluminum sulfide and/or iron sulfide into the reaction liquid at the temperature of 75-95 ℃, then adjusting the pH of the reaction liquid to 3.5-5.5, and preserving heat 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; the method is environment-friendly and safe, has low energy consumption, and can produce high-purity 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, relates to a production method of battery-grade ferrous chloride, 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. The waste acid is generally treated by combustion to convert it into iron oxide, but this method is energy-consuming and has high C emission, which is not environmentally friendly.
With the market share of new energy automobiles becoming larger and larger, the demand of lithium ion batteries also becomes higher and higher, and lithium iron phosphate batteries are common lithium ion batteries. An important raw material for producing lithium iron phosphate is battery-grade iron phosphate, and one of the preparation routes of the battery-grade iron phosphate is a method for preparing the battery-grade iron phosphate by multi-stage reaction disclosed in CN107285292A, namely, ferric phosphate is generated by reacting ferric chloride with a phosphorus salt. And reacting the ferric phosphate with lithium carbonate to obtain the lithium iron phosphate. The lithium iron phosphate electrode material is prepared from raw materials with high demand, the finished product of commercially available ferrous chloride is high in price and low in purity, the contents of chromium and copper impurities are both greater than 20ppm, if an environment-friendly method can be adopted to convert acid liquor generated after cold-rolled steel is continuously pickled into high-purity battery-grade ferrous chloride with the contents of chromium and copper both less than 10ppm, and the high-purity battery-grade ferrous chloride is further oxidized into battery-grade ferric chloride, so that the high-purity battery-grade ferric phosphate is produced from the raw materials, the commercial utilization value of waste acid is greatly improved, the service life of a lithium iron phosphate battery can be remarkably prolonged, and the requirements of new energy automobile batteries are completely met.
However, the prior art does not disclose how to produce the battery-grade ferrous chloride meeting the requirement of the lithium iron phosphate electrode material by using the waste acid solution generated after the cold-rolled steel is continuously acid-washed by an environment-friendly method.
Disclosure of Invention
In order to solve the technical problems, the invention provides a production method of battery-grade ferrous chloride; 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.
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 80-98 ℃, 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) adding aluminum sulfide and/or iron sulfide into the reaction liquid at the temperature of 75-95 ℃, then adjusting the pH of the reaction liquid to 3.5-5.5, and preserving heat 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 3-5 g/L, and the content of iron is 140-190 g/L.
In the step (2), the solid-to-liquid ratio of aluminum sulfide, iron sulfide or the sum of aluminum sulfide and iron sulfide to the reaction solution is 1 g: 1000-100000 mL.
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 (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 production 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 ferrous phosphate and further preparing the lithium iron phosphate electrode material for the battery.
The method for producing battery-grade ferrous chloride from cold-rolled steel pickling waste acid comprises the steps of heating the cold-rolled steel pickling waste acid with the iron content of 50-135 g/L and the hydrogen chloride content of 10-60 g/L to 80-98 ℃, and feeding the cold-rolled steel pickling waste acid into a furnaceIn a container filled with scrap iron, waste acid and the scrap iron react in the container, and free HCl content in reaction liquid after the reaction is 3-5 g/L and iron content is 140-190 g/L; then adding aluminum sulfide and/or iron sulfide into the reaction liquid at the temperature of 75-95 ℃, wherein in the process, taking the aluminum sulfide as an example, in a hot ferrous chloride solution, the sulfide reacts as follows: al (aluminum) 2 S 3 +6H 2 O＝2Al(OH) 3 +3H 2 S, namely, the aluminum sulfide is added and then hydrolyzed to form aluminum hydroxide and hydrogen sulfide.
And then, after the pH value of the reaction solution is adjusted to 3.5-5.5 by using alkaline salt, aluminum hydroxide is insoluble and precipitated under the weak acid condition, the surface area of the precipitate is very large, and the solution can be purified by adsorbing impurities. The formed hydrogen sulfide, copper ions, chromium ions, lead ions and the like are easy to form sulfide precipitates, and then the ferrous chloride solution is purified. The aluminium hydroxide formed after hydrolysis can also act as a flocculant to accelerate precipitation, and the supernatant does not introduce other elements to contaminate the solution.
Then adding flocculating agent into the reaction liquid after cooling the reaction liquid to further 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 less than 10ppm and 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. the invention adopts the aluminum sulfide and/or the ferric sulfide which are not easy to volatilize, the aluminum sulfide and/or the ferric sulfide can react with waste acid after the scrap iron reaction to form aluminum hydroxide and hydrogen sulfide, the hydrogen sulfide and copper ions, chromium ions, lead ions and the like can easily form sulfide precipitates, and then the ferrous chloride solution is purified, the aluminum hydroxide can be used as a flocculating agent to accelerate the precipitation, and the supernatant fluid does not introduce other elements to pollute the solution;
3. 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 cold-rolled steel strips made of plain carbon steel.
Example 1
A production method of battery-grade ferrous chloride is characterized by comprising the following steps:
(1) heating waste acid with the iron content of 115g/L and the hydrogen chloride content of 50g/L, the copper ion content of 38ppm and the chromium ion content of 35ppm to 85 ℃, then sending the waste acid into a container filled with scrap iron to react with the scrap iron for 10 hours, and collecting reaction liquid passing through the container, wherein the iron content of the reaction liquid is 150g/L and the hydrogen chloride content of the reaction liquid is 5 g/L;
(2) adding 32mg of aluminum sulfide into each liter of reaction solution, then adding ammonium bicarbonate without stirring, and under the stirring of carbon dioxide gas, enabling the pH value of the solution to be 5.0;
(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 2
A production method of battery-grade ferrous chloride is characterized by comprising the following steps:
(1) heating waste acid with the iron content of 115g/L and the hydrogen chloride content of 50g/L, the copper ion content of 53ppm and the chromium ion content of 25ppm 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 iron content of the reaction liquid is 150g/L and the hydrogen chloride content of the reaction liquid is 4 g/L;
(2) adding 22mg of aluminum sulfide into each liter of reaction solution, then adding ammonium bicarbonate without stirring, and under the stirring of carbon dioxide gas, enabling the pH value of the solution to be 5.2;
(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 3
A production method of battery-grade ferrous chloride is characterized by comprising the following steps:
(1) heating waste acid with the iron content of 115g/L and the hydrogen chloride content of 50g/L, the copper ion content of 28ppm and the chromium ion content of 42ppm to 85 ℃, then sending the waste acid into a container filled with iron filings to react with the iron filings for 18 hours, and collecting reaction liquid passing through the container, wherein the iron content of the reaction liquid is 150g/L and the hydrogen chloride content of the reaction liquid is 3 g/L;
(2) adding 45mg of aluminum sulfide into each liter of reaction solution, then adding ammonium bicarbonate without stirring, and under the stirring of carbon dioxide gas, enabling the pH value of the solution to be 5.3;
(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.
The content of each substance in the battery-grade ferrous chloride solution prepared in each example is shown in table 1:
TABLE 1
| Element(s) | Unit of | Example 1 | Example 2 | Example 3 | Downstream enterpriseIndustry requirements |
| Fe 2+ | mol/L | 2.415 | 2.518 | 2.451 | 1.8mol/L or more |
| K + | ppm | 61 | 52 | 55 | |
| Na + | ppm | 181 | 170 | 85 | |
| Pb 2+ | ppm | 12 | 8 | 9 | |
| Zn 2+ | ppm | 6.6 | 9.1 | 8.3 | |
| Mg 2+ | ppm | 41 | 8 | 7 | |
| Mn 2+ | ppm | 381 | 377 | 351 | |
| Ca 2+ | ppm | 61 | 15 | 21 | |
| Ni 2+ | ppm | 9.1 | 6.1 | 8.2 | |
| Cr 2+ | ppm | 7.9 | 6.3 | 5.9 | <10ppm |
| Cu 2+ | ppm | 5.4 | 7.5 | 5.5 | <10ppm |
The above detailed description of a method for producing battery grade ferrous chloride 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 may be made without departing from the general inventive concept within the scope of the present invention.
Claims (10)
1. A production method of battery-grade ferrous chloride is characterized by comprising the following steps:
(1) heating cold rolled steel pickling waste acid to 80-98 ℃, 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) adding aluminum sulfide and/or iron sulfide into the reaction liquid at the temperature of 75-95 ℃, then adjusting the pH of the reaction liquid to 3.5-5.5, and preserving heat 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 production 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 production method according to claim 1, wherein in the step (1), the time for passing the heated waste acid through the container filled with the iron pieces is 5 to 25 hours.
4. The production process according to claim 1, wherein in the step (1), the reaction solution passed 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 production method according to claim 1, wherein in the step (2), the solid-to-liquid ratio of aluminum sulfide, iron sulfide, or the sum of aluminum sulfide and iron sulfide to the reaction solution is 1 g: 1000-100000 mL.
6. The production method according to claim 1, wherein in the step (2), the pH of the reaction solution passed through the vessel is adjusted to 3.5 to 5.5 using an alkaline salt.
7. The production method according to claim 5, wherein the basic salt is any one or more of sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
8. The production method according to claim 1, wherein 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 the step (3), if Fe is contained 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. The production method according to any one of claims 1 to 9, which produces battery-grade ferrous chloride.
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