70results about "Cobalt sulfates" patented technology

The invention belongs to the technical field of waste battery recovery and regeneration, and particularly relates to a method for recovering valuable metal from a waste lithium battery positive electrode material. The method comprises the following steps: carrying out sulfuration roasting on waste positive electrode powder, selectively extracting lithium in a water leaching manner, and precipitating lithium to obtain lithium carbonate; separating and purifying the nickel, the cobalt and the manganese through microwave acid leaching, precipitation impurity removal and step-by-step extraction to obtain extract liquor of the nickel, the cobalt and the manganese, and performing reverse extraction on the extract liquor to obtain battery-grade cobalt sulfate, battery-grade nickel sulfate and battery-grade manganese sulfate. According to the method, lithium is extracted firstly, the influence of the lithium element on subsequent nickel-cobalt-manganese extraction is reduced, meanwhile, the recovery rate of lithium is increased through the water leaching method, and the recovery cost is reduced. According to the method, precipitation and impurity removal are performed before nickel-cobalt-manganese extraction, so that the content of impurities in a sulfate solution is reduced, and the recovery rate of nickel, cobalt and manganese is greatly improved.

The invention relates to a battery material preparation technology, in particular to a method for preparing high-purity cobaltous sulfate from crude cobaltous hydroxide, which comprises the following steps: S1, reacting the crude cobaltous hydroxide with sulfuric acid to generate magnesium sulfate; s2, washing to remove magnesium; s3, adding sulfuric acid and hydrogen peroxide into the crude cobalt hydroxide after magnesium washing; adding crude cobalt hydroxide to adjust the pH value to obtain a purified solution; s4, adding sodium fluoride into the purified liquid, and filtering after reaction to obtain filtrate; s5, saponifying with sodium hydroxide by using an acidic extractant, then performing soap conversion by using a cobalt sulfate solution, extracting manganese in the filtrate by using an obtained organic phase, and then performing reverse extraction on the organic phase by using sulfuric acid to obtain a manganese sulfate solution; s6, the raffinate obtained after manganese extraction is introduced into an adsorption tower loaded with a zirconium-based composite fluorine adsorbent; and S7, concentrating and crystallizing the defluorinated solution. According to the method, the zirconium-based composite fluorine adsorbent is introduced to be coupled with the process, fluorine ions can be removed, and cobalt loss caused by cobalt fluoride precipitation and the influence of the fluorine ions on the quality of a cobalt sulfate product are avoided.

A method of preparing a cathode active material composition involves combining a first cathode active material including recycled lithium 40 with a second cathode active material 41; wherein the ratio

Provided is a method for separating impurities and cobalt without using an electrolysis process from a cobalt chloride solution containing impurities and producing a high purity cobalt sulfate. The production method for cobalt sulfate includes: a copper removal step (S1) of adding a sulfurizing agent to a cobalt chloride solution containing one or more impurities of copper, zinc, manganese, calcium, and magnesium and generating a precipitate of sulfide of copper to separate to remove copper; a neutralization step (S2) of adding a neutralizer or a carbonation agent to a cobalt chloride solution having undergone through the copper removal step (S1) and generating cobalt hydroxide or basic cobalt carbonate to separate magnesium; a leaching step (S3) of adding sulfuric acid to the cobalt hydroxide or the basic cobalt carbonate to obtain cobalt sulfate solution; and a solvent extraction step (S4) of bringing an organic solvent containing an alkyl phosphoric acid-based extractant to the cobalt sulfate solution and extracting zinc, manganese, and calcium into the organic solvent to separate to remove zinc, manganese, and calcium. These steps are sequentially executed.

A treatment process for crystallizing a metal sulfate involving pre-treating a feedstock comprising calcium, magnesium, and / or lithium impurities, the pre-treating involving pre-leaching the feedstock in the presence of a lixiviant, selectively extracting a first portion of any of the impurities from the feedstock, and forming a leached solution comprising an uncrystallized metal sulfate and any remaining impurities; and / or refining the leached solution and removing a second portion of any of the remaining impurities; and crystallizing the uncrystallized metal sulfate from the leached solution to form a crystallized metal sulfate. So processed, the crystallized metal sulfate may be battery-grade or electroplating-grade.

The invention discloses a method for purifying metal impurities in cobaltous sulfate, a pure cobaltous sulfate product and application of the pure cobaltous sulfate product, and the purification method comprises the following steps: 1) evaporating a cobaltous sulfate aqueous solution to a supersaturated state, cooling and crystallizing, and heating; and 2) carrying out solid-liquid separation to obtain crystals and mother liquor. By adopting the purification method disclosed by the invention, the content of each metal impurity in the cobaltous sulfate is reduced to be below 100ppb, and the use requirements of the electroplating liquid for cobalt interconnection of the integrated circuit are met.

Provided is a method for separating impurities and cobalt without using an electrolysis process from a cobalt chloride solution containing impurities and producing a high purity cobalt sulfate. The production method includes: a first solvent extraction step (S1) of bringing an organic solvent containing an alkyl phosphoric acid-based extractant into contact with a cobalt chloride solution containing impurities, and extracting zinc, manganese, and calcium into the organic solvent to separate to remove zinc, manganese, and calcium; a copper removal step (S2) of adding a sulfurizing agent to a cobalt chloride solution and generating a precipitate of sulfide of copper to separate to remove copper; a second solvent extraction step (S3) of bringing an organic solvent containing a carboxylic acid-based extractant into contact with a cobalt chloride solution and back extracting cobalt with sulfuric acid after extracting cobalt into the organic solvent to obtain cobalt sulfate solution; and a crystallization step (S4) of the cobalt sulfate solution obtained after having undergone through the second solvent extraction step (S3). These steps are sequentially executed. Without using an electrolysis process, a high purity cobalt sulfate is directly produced by separating cobalt and impurities containing manganese.

This invention belongs to the field of secondary battery cathode material recycling technology. More specifically, it relates to a plasma-sulfate combined method for recycling ternary battery cathode materials. The specific recycling method of this invention includes: immersing the cathode sheet in the solvent N-methylpyrrolidone, ultrasonically treating it to separate the active material layer on the cathode sheet surface from the current collector aluminum foil, sieving to remove the separated current collector aluminum foil, obtaining the cathode material; transferring the cathode material into a microwave reactor, heating it to 450-500℃ in a nitrogen atmosphere, holding the temperature for 10-20 minutes, cooling, and discharging to obtain pyrolysis material; transferring the pyrolysis material to a plasma chamber, using a reducing gas as plasma, and plasma treating it for 20-30 minutes under conditions of a gas pressure of 50-60 Pa and a radio frequency power of 480-550 W to obtain reduced material; using a compound acid leaching solution as the leaching solution, mixing it with the reduced material, and acid leaching for 45-80 minutes to obtain the leaching solution.

The invention provides a method for recycling metal from a waste ternary lithium battery positive electrode material. The method comprises the following steps: mixing the waste ternary lithium battery positive electrode material, a binder, a conductive agent and an organic solvent to prepare mixed slurry; coating a current collector with the mixed slurry to obtain an electrode plate; taking the electrode plate as an anode, taking an inert electrode as a cathode, dividing the electrolytic tank into an anode chamber and a cathode chamber by adopting a lithium ion selective permeable membrane, and carrying out oxidation-reduction reaction, so that transition metal ions are dissolved out from electrolyte of the anode chamber, and lithium phosphate precipitates are formed in the cathode chamber; and carrying out post-treatment on the electrolyte in the anode chamber to obtain the nickel-cobalt mixed metal salt. According to the method, the problems of low lithium purity, incomplete transition metal separation, complex process and the like in the traditional recovery technology are solved, and an efficient, environment-friendly and controllable process path is provided for high-valued recovery of valuable metals of the waste ternary lithium batteries.

In the recovery method provided in this application, CO is generated by the reaction of oxalic acid and concentrated sulfuric acid. This provides an acidic atmosphere for the reaction between the cathode powder and CO, allowing some of the cathode powder (LiMeO2) to melt, transforming the solid-gas two-phase system into a solid-gas-liquid three-phase system, which is beneficial for improving the recovery rate of Li ions in LiMeO2. Furthermore, the use of CO for pre-lithiation results in a low lithium content in the solid filter material, minimizing interference from lithium ions in impurity removal and providing the possibility for subsequent efficient impurity removal. On the other hand, under acidic conditions, CO undergoes a reduction reaction with the cathode powder, reducing high-valence ions in the cathode powder to lower-valence ions, resulting in a more thorough reduction. This allows the solid filter material to dissolve in sulfuric acid, achieving efficient impurity removal. Additionally, Al is removed by adding alkali, oxidant, fluoride, and adsorbent. 3+ Fe 3+ Ca 2+ Mg 2+ F ‑ A second solution containing MeSO4 is obtained, which can be used as a precursor for preparing positive electrode active materials. It achieves efficient overall impurity removal and improves lithium recovery rate, while obtaining a high-purity MeSO4 solution.

The present invention relates to a method for extracting metals from the black mass of lithium-ion batteries, the black mass containing the anode and cathode materials of the batteries, and the cathode material comprising lithium and nickel. Further, the invention relates to an arrangement that is suitable for use in the method.

This invention belongs to the field of phosphorus removal technology, and specifically relates to a deep phosphorus removal method for cobalt sulfate solution through multi-stage synergistic treatment. This invention relates to a deep phosphorus removal method for cobalt sulfate solution through multi-stage synergistic treatment, comprising the following steps: S11. Pretreatment and primary phosphorus removal; S12. Synergistic extraction; S13. Deep purification with resin; S14. Evaporation and crystallization: the exchange liquid obtained in step S13 is concentrated, crystallized, filtered, and washed to obtain cobalt sulfate heptahydrate, and the mother liquor is returned to step S11 for recycling; S15. Phosphorus recovery from phosphorus-containing liquid. The beneficial effects of this invention are: (1) Impurity phosphorus can be deeply purified, and the phosphorus content of the prepared cobalt sulfate heptahydrate is ≤0.00003wt% using the deep phosphorus removal method for cobalt sulfate solution through multi-stage synergistic treatment; (2) The process is mild and easy to promote and apply; (3) The resource utilization of solid waste iron slag transforms solid waste into intermediate products, increasing economic value.

The application provides a treatment method of nickel cobalt hydroxide, comprising the following steps: a first leaching process, reducing and acid leaching the nickel cobalt hydroxide to obtain a leaching solution; a neutralization process, adding a neutralizing agent to the leaching solution to obtain a neutralized solution; a first sulfuration process, adding a first sulfuration agent to the neutralized solution to obtain a first sulfuration solution; a second sulfuration process, adding a second sulfuration agent to the first sulfuration solution to obtain a second sulfuration precipitate; an ion exchange process, adding an ion exchange solution to the second sulfuration precipitate to obtain a third sulfuration precipitate; and a second leaching process, mixing the third sulfuration precipitate with a solvent and oxygen to perform pressurized leaching, and then obtaining a metal salt solution, wherein the metal salt comprises at least one of a nickel salt, a cobalt salt and a manganese salt. The treatment method provided in the embodiments of the application can remove metal impurities such as calcium and magnesium, so that a product containing nickel, cobalt and / or manganese is obtained.

The invention discloses a method for preparing a cobaltous sulfate solution and cobaltous sulfate crystals by using cobalt-containing solid raw materials, which comprises the following steps of: carrying out slurrying pretreatment on the cobalt-containing solid raw materials such as cobalt concentrate, cobalt slag or waste lithium battery positive electrode materials and the like as starting materials; through continuous operation of multi-stage dissolution and multi-stage iron removal (an oxygen and sodium carbonate iron removal system is adopted to replace a traditional sodium hypochlorite and sodium carbonate iron removal system), the cobalt leaching rate is larger than or equal to 97%; subsequently, P204 extraction and impurity removal, P507 nickel-cobalt separation, oil removal and purification are carried out, and a high-quality cobalt sulfate solution is obtained; the solution can be directly supplied to a ternary product production line in a short distance (less than or equal to 8km), or through MVR evaporation concentration, Olso cooling crystallization, centrifugal separation and drying, cobalt sulfate crystals suitable for long-distance transportation are obtained. Meanwhile, MVR evaporation condensate water and high-impurity centrifugal mother liquor are returned to be used for preparing reverse extraction acid needed by P507 extraction, dryer steam condensate water is returned to be used for heating of the slurrying procedure, cyclic utilization of water resources and energy in the whole process is achieved, and the method is suitable for industrial production of high-quality cobalt sulfate products.

A method for preparing battery-grade cobalt sulfate by multistage extraction, comprising the following steps: (1) P204 extraction: uniformly mixing P204 extractant and diluent, saponification treatment, clarification, adding cobalt sulfate solution to be extracted, multistage extraction, oil removal, and obtaining raffinate; (2) Cyanex272 extraction: uniformly mixing Cyanex272 extractant and diluent, saponification treatment, clarification; A section: adding the obtained saponification cobalt extraction organic phase into the raffinate, multistage extraction, stripping; B section: adding the obtained saponification cobalt extraction organic phase into the stripping cobalt sulfate solution obtained in the A section, multistage extraction, stripping, oil removal, evaporation crystallization, and the battery-grade cobalt sulfate is obtained. The cobalt sulfate crystal obtained by the method meets the quality requirements of battery cobalt sulfate type II in the national standard, cobalt and calcium and magnesium are completely separated, the purity and yield of cobalt sulfate are high, the process is simple and short, other impurities are not introduced, it is green and environmental protection, the cost is low, and it is suitable for industrial production.

A method of recycling a waste battery cathode material comprising lithium and at least one of nickel, cobalt and / or manganese, the method comprising: heating the waste battery cathode material in a reducing atmosphere to form a heat-treated waste battery cathode material comprising LiF and one or more of LijO, LiOH, and LijCOs; washing the heat-treated waste battery cathode material in an aqueous solvent to extract both lithium containing species and fluorine containing species, wherein the aqueous solvent does not contain an alkaline earth hydroxide or other species intended to reduce or prevent soluble fluorine species remaining dissolved in the aqueous solvent; separating the aqueous solvent comprising lithium and fluorine species from the heat-treated waste battery material; after separating the aqueous solvent comprising lithium and fluorine species from the heat-treated waste battery material, treating the aqueous solvent to separate lithium species from fluorine species; recovering the lithium species as lithium hydroxide or lithium carbonate; forming an acidic aqueous recycling feed comprising one or more of nickel, cobalt and / or manganese by leaching the heat-treated waste battery cathode material with an inorganic acid after the step of separating the aqueous solvent from the heat-treated waste battery material; and recovering one or more of nickel, cobalt and / or manganese from the acidic aqueous recycling feed via one or more further process steps selected from solvent extraction, solid phase extraction, electrochemical extraction, and precipitation processes.

The present invention provides a controlled autoclave dissolution of metal powders for producing high-purity metal sulphate solutions, comprising the steps of: a. reacting an aqueous slurry comprising a metal powder with sulphuric acid in an autoclave section comprising one or more autoclave reactors at a temperature between 100°C and 250°C, thereby forming a metal sulphate solution having a residual amount of metal powder, whereby the molar ratio of sulphuric acid and metal in said autoclave section is lower than 1.0; and b. separating said metal sulphate solution from said residual metal powder.

The application belongs to the technical field of battery material recycling, and particularly discloses a battery black powder recycling method. The battery black powder recycling method provided by the application comprises the following steps: obtaining lithium-containing leaching liquor and leaching residue by pressurized acid leaching of battery black powder; performing acid leaching reaction on the leaching residue to obtain nickel-, cobalt- and manganese-containing leaching liquor; adding an oxidizing agent to the nickel-, cobalt- and manganese-containing leaching liquor, adjusting the pH by using alkali to remove iron and aluminum, and filtering to obtain a post-iron-and-aluminum-removal liquid; extracting Ca by using HBL120 extractant to obtain Co-, Ni- and Mn-containing raffinate; extracting Mn by using P204 extractant to obtain Mn-loaded organic phase and Co- and Ni-containing raffinate; extracting Co by using Cy272 extractant to obtain Co-loaded organic phase and Ni-containing raffinate; and removing F and P from the Ni-containing raffinate to obtain a nickel sulfate solution. The application has high lithium extraction rate and shortens the process flow of manganese recycling.

The invention discloses a solid-state battery material recovery method, and relates to the technical field of solid-state battery recovery, and the method comprises the following steps: heating first mixed powder in air to obtain second mixed powder; the second mixed powder is leached through organic weak acid and a reducing agent, first leaching residues and first leaching liquid are obtained, and then the first leaching liquid is processed through a wet process; the first leaching residues are leached with sulfuric acid, and second leaching residues and second leaching liquid are obtained; precipitating lanthanum oxalate from the second leaching solution to obtain a first mixed solution; precipitating lithium carbonate from the first mixed solution; the second leaching residues are leached with hydrofluoric acid, and third leaching liquid and carbon are obtained; precipitating zirconium oxalate from the third leaching solution to obtain a second mixed solution, and concentrating the second mixed solution to obtain fluosilicic acid. Through heating, step-by-step leaching, a wet process, precipitation separation and the like, valuable metals, silicon and carbon are efficiently separated and recycled, copper and aluminum impurities are removed, the resource utilization rate is effectively increased, and the feasibility of industrialization is remarkably improved.

The invention provides a recycling method of ternary black powder lithium extraction slag, which comprises the following steps: mixing ternary black powder lithium extraction slag, a pH regulator, a reducing agent and a solvent under normal pressure, carrying out first-stage leaching reaction, and carrying out solid-liquid separation to obtain first-stage leachate and first-stage leaching slag; in the oxygen atmosphere, the first-stage leaching residues and acid liquor are mixed at high pressure, a second-stage leaching reaction is conducted, and second-stage leaching liquid and second-stage leaching residues are obtained after solid-liquid separation; mixing the first-stage leachate, the second-stage leachate, an oxidizing agent and a neutralizing agent, and carrying out precipitation reaction to obtain a solution with iron and aluminum removed; and sequentially carrying out impurity extraction and nickel-cobalt extraction separation on the solution subjected to iron and aluminum removal to respectively obtain a nickel salt solution and a cobalt salt solution. According to the combined process provided by the invention, the problem of low leaching rate of high-valence oxides of nickel, cobalt and manganese in the lithium extraction slag is solved, and efficient separation and purification of nickel, cobalt and manganese are realized; the process is economical, efficient and short in flow and has good application potential.

This invention discloses a method for treating battery black powder and a wastewater treatment device, comprising: reacting battery black powder with a leaching agent to obtain a leachate containing multiple soluble metal salts, wherein the multiple soluble metal salts include lithium; separating the multiple soluble metal salts by means of extraction, and obtaining raffinate wastewater containing the separated lithium; performing a primary pretreatment on the raffinate wastewater; inputting the pretreated wastewater into an oxidation and hydrogen production system for oxidation treatment and electrolytic hydrogen production; performing a secondary pretreatment on the wastewater after oxidation treatment and electrolytic hydrogen production; performing lithium precipitation treatment on the pretreated wastewater; and performing post-treatment on the wastewater after lithium precipitation treatment to meet the required wastewater discharge and / or recyclable material recovery standards; wherein the oxidation and hydrogen production system includes an electrolyzer, a DC power supply, and a hydrogen storage tank.

To provide a method and equipment for extracting a metal from a black aggregate of a lithium ion battery.SOLUTION: The black agglomerates contain the anode and cathode materials of the battery and some copper, with the cathode materials including lithium and nickel. Furthermore, the invention relates to an installation suitable for use in the method.SELECTED DRAWING: None

A green chemistry hydrometallurgical process for recovering one or more metals from a metal-containing material includes leaching the metal-containing material with formic acid, obtaining a leachate comprising the one or more metals as one or more metal formates, and precipitating at least one of the one or more metal formates. The metal-containing material may be a lithium-ion battery cathode material, resulting in Li formate remaining in solution and precipitation of salts including one or more of Ni, Co, and Mn formates. Steps may include filtration of the leachate, sulphurization of retained metal formate salts to produce metal sulphate salts, purification of filtered leachate by adding lithium carbonate and filtering, dewatering of the purified leachate, and thermal decomposition of resulting lithium salts to produce battery grade lithium carbonate. Carbon dioxide, water, and formic acid may be recovered and reused, without liquid or solid waste produced.

The present invention provides a multi-stage solvent extraction process for selectively extracting cobalt from an aqueous mixed metal solution comprising nickel and cobalt, whereby each solvent extraction stage is characterized by maintaining a magnesium concentration in an aqueous phase above a predetermined magnesium concentration.

The invention provides a high-purity cobalt sulfate solution as well as a preparation method and application thereof. The preparation method comprises the following steps: by taking a cobalt plate as an anode, an inert metal plate as a cathode and a dilute sulfuric acid solution as an electrolyte, carrying out electrolysis in an electrolytic bath to obtain a cobalt sulfate stock solution, and filtering to obtain the high-purity cobalt sulfate solution. According to the technical scheme, synthesis and preliminary purification of the cobalt sulfate solution can be achieved at the same time, the process is simple, parameters are easy to control, efficiency is high, meanwhile, the content of key impurity elements such as Fe, Ni, Cu and Pb in the prepared cobalt sulfate solution is lower than 50 ppb, and the purity requirement of the electroplating solution for cobalt interconnection of an integrated circuit is met.

The invention belongs to the technical field of environmental engineering and resource recycling, and particularly relates to a gradient recycling method for fluorine and heavy metal in fluorine-containing heavy metal waste liquid. The method comprises the following steps: pretreating the fluorine-containing heavy metal waste liquid, mixing the pretreated waste liquid with soluble calcium salt, and carrying out a precipitation defluorination reaction to obtain calcium fluoride and defluorination waste liquid; adjusting the pH value of the defluorination waste liquid to be greater than or equal to 9, and carrying out precipitation reaction to obtain heavy metal hydroxide precipitate and treated waste liquid; and the heavy metal hydroxide precipitate is subjected to acid dissolution, solvent extraction separation, reverse extraction and electrolysis or salification, and a metal copper elementary substance, a metal nickel elementary substance and a cobalt salt product are obtained. According to the method provided by the invention, cascade separation of fluorine and heavy metal elements can be realized, the separation selectivity is good, the recovery rate and purity of heavy metal and fluorine are high, and the technical problems of poor separation selectivity, low resource recovery purity and low value-added utilization degree in the existing fluorine-containing heavy metal waste liquid treatment are solved.

The present disclosure discloses a wet process for recovering valuable metals from a lithium battery. In the method, a waste lithium battery powder is subjected to selective leaching under the condition that a hydrogen sulfide gas is introduced through pressurization, such that Mn2+, Li+, and Al3+ metal ions enter a first-stage leaching liquor and nickel, cobalt, copper, and iron exist in a first-stage leaching residue in the form of a sulfide; then a pH of the first-stage leaching liquor is adjusted to remove aluminum and manganese, which achieves extremely thorough metal separation and leads to relatively pure products; a first-stage leaching residue is subjected to leaching in an acid liquor under a negative pressure, such that the sulfides of nickel, cobalt, iron, and copper are dissolved in a second-stage leaching liquor, and a hydrogen sulfide gas produced can be recycled in the first-stage leaching procedure through pressurization.

The present invention provides a controlled autoclave dissolution of metal powders for producing high-purity metal sulphate solutions, comprising the steps of: a. reacting an aqueous slurry comprising a metal powder with sulphuric acid in an autoclave section comprising one or more autoclave reactors at a temperature between 100°C and 250°C, thereby forming a metal sulphate solution having a residual amount of metal powder, whereby the molar ratio of sulphuric acid and metal in said autoclave section is lower than 1.0; and b. separating said metal sulphate solution from said residual metal powder.

The invention belongs to the technical field of secondary battery positive electrode material recovery. The invention relates to a recycling method, in particular to a method for recycling a ternary battery positive electrode material by combining plasma with sulfate. The specific recovery method of the product comprises the following steps: soaking a positive pole piece in a solvent N-methyl pyrrolidone, carrying out ultrasonic treatment to separate a surface active material layer of the positive pole piece from a current collector aluminum foil, and screening to remove the separated current collector aluminum foil to obtain a positive pole material; transferring the positive electrode material into a microwave reactor, carrying out microwave heating to 450-500 DEG C in a nitrogen atmosphere, carrying out a heat preservation reaction for 10-20 min, cooling, and discharging to obtain a pyrolysis material; transferring the pyrolysis material to a plasma chamber, and carrying out plasma treatment for 20-30 minutes under the conditions that the air pressure is 50-60 Pa and the radio frequency power is 480-550 W by taking reducing gas as plasma, so as to obtain a reduction material; and the compound acid leaching solution serves as a leaching solution and is mixed with the reduction material, then acid leaching reaction is conducted for 45-80 min, and the leaching solution is obtained.