CN116555570A - Method for leaching valuable metals from ternary black powder under low-temperature low-acid condition - Google Patents
Method for leaching valuable metals from ternary black powder under low-temperature low-acid condition Download PDFInfo
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- CN116555570A CN116555570A CN202310724807.9A CN202310724807A CN116555570A CN 116555570 A CN116555570 A CN 116555570A CN 202310724807 A CN202310724807 A CN 202310724807A CN 116555570 A CN116555570 A CN 116555570A
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- 238000002386 leaching Methods 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000843 powder Substances 0.000 title claims abstract description 54
- 239000002253 acid Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 150000002739 metals Chemical class 0.000 title claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004537 pulping Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 238000007710 freezing Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 64
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 32
- 229910017052 cobalt Inorganic materials 0.000 claims description 32
- 239000010941 cobalt Substances 0.000 claims description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 32
- 229910052748 manganese Inorganic materials 0.000 claims description 32
- 239000011572 manganese Substances 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 230000000630 rising effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 18
- 238000009616 inductively coupled plasma Methods 0.000 description 15
- 238000003860 storage Methods 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000000879 optical micrograph Methods 0.000 description 6
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to the technical field of waste lithium batteries, and in particular discloses a method for leaching valuable metals from ternary black powder under the condition of low temperature and low acid, which comprises the following steps: pulping: mixing ternary black powder with water, and pulping to obtain slurry; primary leaching: adding acid liquor and a reducing agent into slurry obtained by pulping, and reacting at room temperature to perform primary leaching; freezing at low temperature: introducing liquid nitrogen or dry ice into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen when the temperature of the slurry reaches-50 to-60 ℃; deep leaching: heating to melt the frozen polycrystalline ice completely, wherein the process is deep leaching; and (3) filtering: filtering the melted slurry to obtain filter residues and filtrate, washing the filter residues, and combining the filtrate and the washing liquid to obtain the leaching solution. Compared with the traditional leaching technology, the method can reduce the leaching temperature, reduce the consumption of acid and reducing agent, reduce the production cost, reduce the operation difficulty, and improve the leaching rate of valuable metals, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a method for leaching valuable metals from ternary black powder under the condition of low temperature and low acid.
Background
With the rapid development of new energy automobiles, retired and scrapped lithium batteries are more and more, wherein the nickel-cobalt-manganese ternary lithium batteries occupy a larger proportion, and the black mixture obtained after the waste nickel-cobalt-manganese ternary lithium batteries are discharged, disassembled, broken, phenolic acid and separated is called ternary black powder. In order to standardize the development of the lithium battery recovery industry, relevant departments prescribe that the ternary black powder contains a large amount of valuable metals such as nickel, cobalt, manganese and lithium, the recovery rate of nickel, cobalt and manganese is required to exceed 98 percent, and the recovery rate of lithium is required to exceed 85 percent in an enterprise of 'the standard condition of the comprehensive utilization industry of the waste power storage battery of the new energy automobile', so that how to efficiently recover the valuable metals with economic value from the ternary black powder is a difficulty and a hot spot of research and development.
In the prior art, the recovery of valuable metals in ternary black powder mostly adopts wet recovery, the wet recovery has the characteristics of low energy consumption, low cost and low pollution, acid leaching and extraction separation are extremely critical steps in the wet recovery process, and in order to solve the problem of low production efficiency, chinese patent publication No. CN115764036A discloses a method for leaching valuable metals from ternary battery recovered black powder, which comprises the following steps: (1) pretreatment of dynamic reduction roasting: placing black powder recovered from waste nickel-cobalt-manganese ternary lithium batteries in a protective atmosphere dynamic roasting furnace; and (2) extracting lithium by two-stage countercurrent water leaching: mixing the reduction roasting material with pure water according to a ratio of 6-8:1, mixing the liquid and the solid in a mass ratio, and then carrying out a mixing slurrying reaction under the conditions that the temperature is 40-60 ℃ and the reaction time is 30-45 minutes; (3) Normal pressure leaching and high pressure acid leaching are combined with two-stage countercurrent leaching. Namely, the leaching rate of nickel, cobalt, manganese and the like is improved by combining the modes of roasting pretreatment, leaching extraction of lithium element by countercurrent water at two ends, high-pressure acid leaching and the like, however, the operation is more complex, and the production cost is higher.
In the conventional acid leaching process, in order to ensure the leaching rate of nickel, cobalt, manganese and lithium in the ternary black powder, excessive acid and a reducing agent have to be added, in the subsequent impurity removing process, the pH value of the leaching solution is required to be raised to remove impurities such as iron, aluminum and the like, so that if the excessive acid is added in the earlier stage of leaching, a lot of liquid alkali is inevitably wasted to adjust the pH value and remove impurities in the impurity removing process, in addition, in order to improve the leaching rate of nickel, cobalt, manganese and lithium, the leaching process is required to be carried out in a high-temperature environment, and the overflow and the increase of energy consumption are easy to cause.
Therefore, the invention aims to develop a method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions, so as to better solve the problems of low leaching rate, high acid and alkali consumption, easy groove overflow and the like of the valuable metals in the ternary black powder, and better meet the actual production needs.
Disclosure of Invention
The invention aims to solve the technical problems of low leaching rate, high acid consumption, easy groove overflow, high energy consumption and the like of valuable metals in ternary black powder by providing a method for leaching the valuable metals from the ternary black powder under the condition of low temperature and low acid.
The technical problems solved by the invention are realized by adopting the following technical scheme:
a method for leaching valuable metals from ternary black powder comprises pulping ternary black powder, quick-freezing the primarily leached slurry to-50 to-60 ℃ in the leaching process to form polycrystalline ice, and then heating to carry out deep leaching treatment.
Further, the method for leaching valuable metals from ternary black powder comprises the following steps:
pulping: mixing ternary black powder with water, and pulping to obtain slurry;
primary leaching: adding acid liquor and a reducing agent into slurry obtained by pulping, and reacting at room temperature to perform primary leaching;
freezing at low temperature: introducing liquid nitrogen or dry ice into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen or the dry ice when the temperature of the slurry reaches-50 to-60 ℃;
deep leaching: heating to melt the frozen polycrystalline ice completely, wherein the process is deep leaching;
and (3) filtering: filtering the melted slurry to obtain filter residues and filtrate, washing the filter residues, and combining the filtrate and the washing liquid to obtain the leaching solution.
Further, in the pulping step, the solid-to-liquid ratio of the ternary black powder to water is 1:3-6.
Further, in the preliminary leaching step, the acid liquor is concentrated sulfuric acid, and the reducing agent is hydrogen peroxide. Preferably, the sulfuric acid is concentrated sulfuric acid of 98% or more.
Preferably, the mass concentration of the hydrogen peroxide is 27-30%;
further, the amount of sulfuric acid added is 105-110% of theoretical amount, and the amount of hydrogen peroxide added is 150-200% of theoretical value.
Further, the reaction time of the primary leaching is 0.5-1 h.
Further, stirring is maintained in the primary leaching and deep leaching processes, and stirring is stopped in the low-temperature freezing process.
Further, in the deep leaching step, the temperature rising mode is natural temperature rising at room temperature, and the polycrystalline ice is recrystallized in the deep leaching process.
Further, in the obtained leaching solution, the leaching rate of lithium is more than or equal to 99%, the leaching rate of nickel is more than or equal to 99.5%, the leaching rate of cobalt is more than or equal to 99%, and the leaching rate of manganese is more than or equal to 99.5%.
The beneficial effects are that:
the method for leaching valuable metals from ternary black powder under the low-temperature low-acid condition utilizes quick freezing slurry to form polycrystalline ice, then heating to recrystallize the polycrystalline ice, in the recrystallization process, the number of ice crystals is reduced, the ice crystals grow, in the ice crystal evolution process, the surface energy of large ice crystals is smaller than that of small ice crystals, the large ice crystals become larger, the small ice crystals become smaller or even disappear, a liquid layer appears between the ice crystals, and the black powder, acid liquor and reducing agent are enriched in the liquid layer in an ice gap, so that the concentration of the acid liquor and the reducing agent in the liquid layer in the ice gap is extremely high, and the efficient leaching of nickel, cobalt, manganese and lithium in the ternary black powder under the low-temperature low-acid condition is realized.
Compared with the traditional leaching process, the method for leaching valuable metals from ternary black powder under the low-temperature and low-acid condition can reduce the leaching temperature, reduce the consumption of acid and reducing agent, reduce the production cost and energy consumption, reduce the operation difficulty, simultaneously prevent a high Wen Mao tank, improve the leaching rate of the valuable metals, and is suitable for industrial production.
According to the method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions, the leaching rate of lithium in the obtained leaching solution is more than or equal to 99%, the leaching rate of nickel is more than or equal to 99.5%, the leaching rate of cobalt is more than or equal to 99%, and the leaching rate of manganese is more than or equal to 99.5%, so that the method has extremely important economic value.
Drawings
FIG. 1 is an optical microscope image of polycrystalline ice formed from slurry after the slurry was chilled in example 1.
FIG. 2 is an optical microscopic image of the polycrystalline ice formed from the slurry after the natural temperature rise in example 1 was recrystallized.
FIG. 3 is an optical microscope image of polycrystalline ice formed from the slurry after the temperature reduction and freezing in example 2.
FIG. 4 is an optical microscopic image of the polycrystalline ice formed from the slurry after the natural temperature rise in example 2 was recrystallized.
Detailed Description
In order that the manner in which the invention is attained, as well as the features and advantages thereof, will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions comprises the following steps:
pulping: uniformly mixing black powder of the nickel-cobalt-manganese ternary lithium ion battery, and measuring the content of each component by ICP (inductively coupled plasma) as follows: lithium 5.4%, nickel 22.1%, cobalt 8.5%, manganese 11.5%; weighing 100g of mixed powder, putting into a beaker, adding 300g of water, and uniformly stirring to obtain slurry;
primary leaching: 123.2g of 98% concentrated sulfuric acid and 70.4g of 27.5% hydrogen peroxide are added into the slurry obtained by pulping, and stirring reaction is carried out for 1h at normal temperature;
freezing at low temperature: introducing liquid nitrogen into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen when the temperature of the slurry reaches-50 to-60 ℃;
deep leaching: naturally heating at room temperature after stopping adding liquid nitrogen, recrystallizing the polycrystalline ice due to the temperature rise, and enriching substances, sulfuric acid and hydrogen peroxide in ternary black powder in a liquid layer in an ice joint in the recrystallization process, wherein the process is deep leaching; when the polycrystalline ice is completely melted, finishing deep leaching;
and (3) filtering: filtering the slurry subjected to deep leaching to obtain filter residues and filtrate; and (3) continuously cleaning filter residues with 300g of water, stirring for 0.5h, filtering, taking the filter residues as a recovered negative electrode, combining the filtrate and the filtered washing liquid to obtain a leaching solution, and putting the leaching solution into a leaching solution storage barrel.
The total volume of the leachate and the washing solution in the leachate storage bucket was measured to be 590mL, and the concentration of lithium, nickel, cobalt and manganese in the solution was detected by ICP, wherein the concentration of lithium was 9.1g/L, the concentration of nickel was 37.3g/L, the concentration of cobalt was 14.3g/L and the concentration of manganese was 19.5g/L.
The leaching rates of lithium nickel cobalt manganese are calculated as follows: 99.4% of lithium, 99.6% of nickel, 99.3% of cobalt and 100% of manganese.
In the embodiment, the whole process is performed at a lower temperature, so that the energy consumption is lower, and phenomena such as groove overflow and the like can be effectively prevented. The optical microscope image of the polycrystalline ice formed by the slurry is shown in figure 1, and after natural temperature rise, the optical microscope image of the polycrystalline ice formed by the slurry is shown in figure 2, which shows that in the recrystallization process, because the surface energy of large ice crystals is smaller than that of small ice crystals, the large ice crystals become larger, the small ice crystals become smaller or even disappear, a liquid layer appears between the ice crystals, and black powder, acid liquor and a reducing agent are enriched in the liquid layer in an ice gap, so that the concentration of the acid liquor and the reducing agent in the liquid layer in the ice gap is extremely high, and the high-efficiency leaching of nickel, cobalt, manganese and lithium in the ternary black powder under the low-temperature low-acid condition is realized.
Example 2
A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions comprises the following steps:
pulping: uniformly mixing black powder of the nickel-cobalt-manganese ternary lithium ion battery, and measuring the content of each component by ICP (inductively coupled plasma) as follows: lithium 5.4%, nickel 22.1%, cobalt 8.5%, manganese 11.5%; weighing 100g of mixed powder, putting into a beaker, adding 600g of water, and uniformly stirring to obtain slurry;
primary leaching: 117.6g of 98% concentrated sulfuric acid and 93.8g of 27.5% hydrogen peroxide are added into the slurry obtained by pulping, and the mixture is stirred and reacted for 0.5h at normal temperature;
freezing at low temperature: introducing liquid nitrogen into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen when the temperature of the slurry reaches-50 to-60 ℃;
deep leaching: naturally heating at room temperature after stopping adding liquid nitrogen, recrystallizing the polycrystalline ice due to the temperature rise, and enriching substances, sulfuric acid and hydrogen peroxide in ternary black powder in a liquid layer in an ice joint in the recrystallization process, wherein the process is deep leaching; when the polycrystalline ice is completely melted, finishing deep leaching;
and (3) filtering: filtering the slurry subjected to deep leaching to obtain filter residues and filtrate; and (3) continuously cleaning filter residues with 600g of water, stirring for 1h, filtering, taking the filter residues as a recovered negative electrode, combining the filtrate and the filtered washing liquid to obtain a leaching solution, and putting the leaching solution into a leaching solution storage barrel.
The total volume of the leachate and the washing solution in the leachate storage bucket was measured to be 1170mL, and the concentration of lithium, nickel, cobalt and manganese in the solution was detected by ICP, wherein the concentration of lithium was 4.6g/L, the concentration of nickel was 18.8g/L, the concentration of cobalt was 7.3g/L and the concentration of manganese was 9.8g/L.
The leaching rates of lithium nickel cobalt manganese are calculated as follows: 99.7% of lithium, 99.5% of nickel, 100% of cobalt and 99.7% of manganese.
In the embodiment, the whole process is performed at a lower temperature, so that the energy consumption is lower, and phenomena such as groove overflow and the like can be effectively prevented. The optical microscope image of the polycrystalline ice formed by the slurry is shown in fig. 3, and after natural temperature rise, the optical microscope image of the polycrystalline ice formed by the slurry is shown in fig. 4, which shows that in the recrystallization process, because the surface energy of large ice crystals is smaller than that of small ice crystals, the large ice crystals become larger, the small ice crystals become smaller or even disappear, a liquid layer appears between the ice crystals, and black powder, acid liquor and reducing agent are enriched in the liquid layer in the ice gap, so that the concentration of the acid liquor and the reducing agent in the liquid layer in the ice gap is extremely high, and the high-efficiency leaching of nickel, cobalt, manganese and lithium in the ternary black powder under the low-temperature low-acid condition is realized.
Comparative example 1
A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions comprises the following steps:
pulping: uniformly mixing black powder of the nickel-cobalt-manganese ternary lithium ion battery, and measuring the content of each component by ICP (inductively coupled plasma) as follows: lithium 5.4%, nickel 22.1%, cobalt 8.5%, manganese 11.5%; weighing 100g of mixed powder, putting into a beaker, adding 600g of water, and uniformly stirring to obtain slurry;
primary leaching: 117.6g of 98% concentrated sulfuric acid and 93.8g of 27.5% hydrogen peroxide are added into the slurry obtained by pulping, and the mixture is stirred and reacted for 0.5h at normal temperature;
and (3) filtering: filtering the slurry subjected to deep leaching to obtain filter residues and filtrate; and (3) continuously cleaning filter residues with 600g of water, stirring for 1h, filtering, taking the filter residues as a recovered negative electrode, combining the filtrate and the filtered washing liquid to obtain a leaching solution, and putting the leaching solution into a leaching solution storage barrel.
The total volume of the leachate and the washing solution in the leachate storage bucket was measured to be 1170mL, and the concentration of lithium, nickel, cobalt and manganese in the solution was detected by ICP, wherein the concentration of lithium was 3.4g/L, the concentration of nickel was 14.6g/L, the concentration of cobalt was 5.8g/L and the concentration of manganese was 8.1g/L.
The leaching rates of lithium nickel cobalt manganese are calculated as follows: 73.7% of lithium, 77.3% of nickel, 79.8% of cobalt and 82.4% of manganese.
Comparative example 2
A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions comprises the following steps:
pulping: uniformly mixing black powder of the nickel-cobalt-manganese ternary lithium ion battery, and measuring the content of each component by ICP (inductively coupled plasma) as follows: lithium 5.4%, nickel 22.1%, cobalt 8.5%, manganese 11.5%; weighing 100g of mixed powder, putting into a beaker, adding 600g of water, and uniformly stirring to obtain slurry;
primary leaching: 117.6g of 98% concentrated sulfuric acid and 93.8g of 27.5% hydrogen peroxide are added into the slurry obtained by pulping, and the mixture is stirred and reacted for 0.5h at normal temperature;
freezing at low temperature: introducing liquid nitrogen into the slurry after primary leaching to freeze the slurry, and stopping adding the liquid nitrogen when the temperature of the slurry reaches-10 to-20 ℃;
deep leaching: naturally heating at room temperature after stopping adding liquid nitrogen, and finishing deep leaching when the polycrystalline ice is completely melted;
and (3) filtering: filtering the slurry subjected to deep leaching to obtain filter residues and filtrate; and (3) continuously cleaning filter residues with 600g of water, stirring for 1h, filtering, taking the filter residues as a recovered negative electrode, combining the filtrate and the filtered washing liquid to obtain a leaching solution, and putting the leaching solution into a leaching solution storage barrel.
The total volume of the leachate and the washing solution in the leachate storage bucket was 1160mL, and the concentration of lithium, nickel, cobalt and manganese in the solution was detected by ICP, wherein the concentration of lithium was 4.2g/L, the concentration of nickel was 16.2g/L, the concentration of cobalt was 6.4g/L and the concentration of manganese was 8.9g/L.
The leaching rates of lithium nickel cobalt manganese are calculated as follows: 90.2% of lithium, 85.0% of nickel, 87.3% of cobalt and 89.8% of manganese.
The leaching effect is not ideal, which indicates that the temperature control of low-temperature freezing is critical.
Comparative example 3
A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions comprises the following steps:
pulping: uniformly mixing black powder of the nickel-cobalt-manganese ternary lithium ion battery, and measuring the content of each component by ICP (inductively coupled plasma) as follows: lithium 5.4%, nickel 22.1%, cobalt 8.5%, manganese 11.5%; weighing 100g of mixed powder, putting into a beaker, adding 600g of water, and uniformly stirring to obtain slurry;
primary leaching: 117.6g of 98% concentrated sulfuric acid and 93.8g of 27.5% hydrogen peroxide are added into the slurry obtained by pulping, and the mixture is stirred and reacted for 0.5h at normal temperature;
freezing at low temperature: introducing liquid nitrogen into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen when the temperature of the slurry reaches-50 to-60 ℃;
deep leaching: immediately placing the solution into a water bath kettle with the temperature of 80 ℃ after stopping adding liquid nitrogen to quickly raise the temperature of the material to 80 ℃, quickly dissolving the formed polycrystalline ice, and finishing deep leaching when the polycrystalline ice is completely melted;
and (3) filtering: filtering the slurry subjected to deep leaching to obtain filter residues and filtrate; and (3) continuously cleaning filter residues with 600g of water, stirring for 1h, filtering, taking the filter residues as a recovered negative electrode, combining the filtrate and the filtered washing liquid to obtain a leaching solution, and putting the leaching solution into a leaching solution storage barrel.
The total volume of the leachate and the washing solution in the leachate storage barrel was measured to be 1060mL, and the concentration of lithium, nickel, cobalt and manganese in the solution was detected by ICP, wherein the concentration of lithium was 4.7g/L, the concentration of nickel was 17.8g/L, the concentration of cobalt was 7.4g/L and the concentration of manganese was 9.9g/L.
The leaching rates of lithium nickel cobalt manganese are calculated as follows: 92.3% of lithium, 85.4% of nickel, 92.3% of cobalt and 91.3% of manganese.
Although the leaching rate of lithium, cobalt and manganese is higher than 90%, the leaching effect of nickel is not ideal, and the whole leaching effect is not ideal. The method is more beneficial to efficient leaching by adopting a natural temperature rising mode in the deep leaching process, and has important influence on the final leaching effect.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method for leaching valuable metals from ternary black powder under the low-temperature and low-acid conditions is characterized in that the ternary black powder is pulped, in the leaching process, the primarily leached pulp is quickly frozen to minus 50 ℃ to minus 60 ℃ to form polycrystalline ice, and then the temperature is raised to carry out deep leaching treatment.
2. The method for leaching valuable metals from ternary black powder under low-temperature and low-acid conditions according to claim 1, comprising the following steps:
pulping: mixing ternary black powder with water, and pulping to obtain slurry;
primary leaching: adding acid liquor and a reducing agent into slurry obtained by pulping, and reacting at room temperature to perform primary leaching;
freezing at low temperature: introducing liquid nitrogen or dry ice into the slurry after primary leaching to enable the slurry to form polycrystalline ice, and stopping adding the liquid nitrogen or the dry ice when the temperature of the slurry reaches-50 to-60 ℃;
deep leaching: heating to melt the frozen polycrystalline ice completely, wherein the process is deep leaching;
and (3) filtering: filtering the melted slurry to obtain filter residues and filtrate, washing the filter residues, and combining the filtrate and the washing liquid to obtain the leaching solution.
3. The method for leaching valuable metals from ternary black powder under the condition of low temperature and low acid according to claim 2, wherein in the pulping step, the solid-to-liquid ratio of the ternary black powder to water is 1:3-6.
4. The method for leaching valuable metals from ternary black powder under the low-temperature and low-acid condition according to claim 2, wherein in the preliminary leaching step, the acid liquor is concentrated sulfuric acid, and the reducing agent is hydrogen peroxide.
5. The method for leaching valuable metals from ternary black powder under low-temperature and low-acid conditions according to claim 4, wherein the amount of sulfuric acid added is 105-110% of theoretical amount, and the amount of hydrogen peroxide added is 150-200% of theoretical amount.
6. The method for leaching valuable metals from ternary black powder under the condition of low temperature and low acid according to claim 2, wherein the reaction time of primary leaching is 0.5-1 h.
7. The method for leaching valuable metals from ternary black powder under low-temperature and low-acid conditions according to claim 2, wherein stirring is maintained during primary leaching and deep leaching, and stirring is stopped during low-temperature freezing.
8. The method for leaching valuable metals from ternary black powder under the low-temperature and low-acid condition according to claim 1, wherein in the deep leaching step, the temperature rising mode is natural temperature rising at room temperature, and the polycrystalline ice is recrystallized in the leaching process.
9. The method for leaching valuable metals from ternary black powder under the low-temperature and low-acid condition according to claim 1, wherein the leaching rate of lithium is more than or equal to 99%, the leaching rate of nickel is more than or equal to 99.5%, the leaching rate of cobalt is more than or equal to 99%, and the leaching rate of manganese is more than or equal to 99.5% in the obtained leaching solution.
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