CN116529401A - Copper removing agent, preparation method thereof and copper removing method - Google Patents
Copper removing agent, preparation method thereof and copper removing method Download PDFInfo
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- CN116529401A CN116529401A CN202380008738.XA CN202380008738A CN116529401A CN 116529401 A CN116529401 A CN 116529401A CN 202380008738 A CN202380008738 A CN 202380008738A CN 116529401 A CN116529401 A CN 116529401A
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- 239000010949 copper Substances 0.000 title claims abstract description 155
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 148
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000002516 radical scavenger Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000001694 spray drying Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000010926 waste battery Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005486 sulfidation Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 and thus Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004137 mechanical activation Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a copper removing agent, a preparation method thereof and a copper removing method, and belongs to the technical field of wet recycling of waste ternary lithium ion battery anode materials. The copper removing agent is prepared from the sulphurized slag generated in the recovery process of the waste batteries, has smaller particle diameter and larger specific surface area, is loose in crystal structure and excellent in activation performance, and is used for removing copper from the battery recovery leaching liquid and has excellent copper removal rate.
Description
Technical Field
The invention relates to the technical field of wet recycling of waste ternary lithium ion battery anode materials, in particular to a copper removing agent, a preparation method thereof and a copper removing method.
Background
In recent years, sales of lithium battery power automobiles in China are increased, the lithium battery power automobiles are limited by service life, and the number of scrapped power batteries is increased. It is predicted that the scrapped amount of the 2027 ternary cathode material and the lithium iron phosphate cathode material can reach 69 ten thousand tons and 26.54 ten thousand tons, so that the power recovery of the waste lithium ion battery is particularly interesting.
At present, the recovery of valuable metals in the power of the waste lithium ion batteries is mainly divided into two types of pyrogenic treatment and wet treatment, and the wet treatment of the waste batteries for recovering the valuable metals has the advantages of environmental friendliness and high recovery rate of the valuable metals, is widely applied at home and abroad, and is a mainstream waste battery recovery process.
The wet treatment process is to leach out metal ions in the waste battery anode material by selecting proper acidic or alkaline medium, and then obtain valuable metals such as lithium, cobalt, manganese and the like by methods such as precipitation, organic matter extraction, separation, purification and the like. In the leaching process, the copper foil in the battery anode material can be inevitably dissolved into the leaching solution, and the removal effect of the copper in the leaching solution directly influences the quality of the product. In addition, as the ternary positive electrode material contains Ni element, ni metal components are also simultaneously present in the waste battery leaching solution.
The main methods of the separation and purification of Cu in the leaching solution in the smelting production of China are a solvent extraction method and a chemical precipitation method. The operation of precipitation copper removal by adopting a vulcanization method is relatively simple, the cost is relatively low, and the process is more mature. In general, the copper removal process of a battery recycling enterprise is carried out by adding excessive sodium sulfide, and the main chemical reaction is as follows: cu (Cu) 2+ +Na 2 S＝＝CuS+2Na + . In addition to CuS, some of nickel in the leachate enters the sulfidic slag, which is finally obtained in the copper removal step, as nickel sulfide.
Along with the increasing recovery of waste batteries, the production amount of the vulcanized slag in the production process is huge, and under the condition of no recovery, the valuable metals contained in the vulcanized slag form larger resource waste.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a copper removing agent which comprises NiS and NiS 2 And CuS, which has excellent copper removal efficiency.
The invention also aims to provide a preparation method of the copper removing agent, wherein the copper removing agent is prepared from the sulphurized slag generated in the recovery process of the waste batteries.
Another object of the invention is to provide a copper removal method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a copper removing agent comprises NiS and NiS 2 And CuS.
The solubility product of NiS and CuS is as follows: ksp (CuS) =9×10 -35 、Ksp(NiS)＝2.8*10 -18 . Therefore, cu exhibits a stronger sulfur affinity than Ni, and thus, copper can be precipitated by using this portion of NiS in the copper scavenger, achieving a good copper removal effect.
Preferably, the copper removing agent comprises the following components in percentage by weight:
NiS 62.5～71.3％，NiS 2 5.5～10.3％，CuS 13.2～18.4％，Cu 2～4.5％，C 0.5～1.8％。
the copper removing agent is prepared from sulfide slag containing nickel and copper and active carbon, wherein the copper removing agent is prepared from NiS and NiS 2 And a small amount of Cu and C in addition to the CuS component.
Preferably, the average particle diameter of the copper scavenger is 40 to 80 μm.
Preferably, the specific surface area of the copper removing agent is 320-500 m 2 /g。
The copper removing agent is granular, has smaller particle diameter and larger specific surface area, has loose crystal structure and excellent activation performance. The average grain diameter of the copper removing agent is 40-80 mu m, and the specific surface area is 320-500 m 2 /g。
The invention also provides a preparation method of the copper removing agent, which comprises the following steps:
s1, mixing active carbon with sulfide slag containing nickel and copper according to a mass ratio of 1: (1-5) mixing and then performing ball milling treatment to obtain powder;
s2, dispersing the powder obtained in the step S1 into sulfuric acid solution for pulping to obtain slurry;
s3, carrying out spray drying on the slurry obtained in the step S2 to obtain a spray-dried material;
s4, roasting the spray-dried material obtained in the step S3 under the protection of inert gas to obtain the copper removing agent.
In the sulfidic slag containing nickel and copper, nickel exists in the form of NiS and copper exists in the form of CuS.
Preferably, the copper content in the vulcanized slag is 7-15%, and the nickel content is 50-60%.
In the preparation method of the copper removing agent, firstly, the activated carbon and the vulcanized slag are mechanically activated by ball milling. On the one hand, the mechanical activation can make the granularity of the vulcanized slag thin, so that the specific surface area of the vulcanized slag is effectively enlarged; on the other hand, the deformation and defects of the internal lattice of the substance are increased, various dislocation is caused, amorphization phenomenon is generated, the energy storage of the substance is increased, the internal energy is increased, and the reactivity of the substance is improved; in addition, the redistribution of ions in the cation-anion superlattice can be caused, and when the crystal size is small enough and the mechanical impact force is large enough for the sulfide slag, the crystal structure distortion is caused, and the physical and chemical properties are distorted.
On the basis of mechanical activation, the powder is pulped by sulfuric acid solution, so that the pulping can fully mix the sulfation slag with carbon powder and sulfuric acid, and the subsequent spray drying and roasting processes are facilitated. In addition, in the presence of sulfuric acid, through subsequent high-temperature reaction, the sulfide slag and the carbon powder can form a series of sulfides, so that the activity of sulfur atoms in the nickel sulfide is enhanced, the nickel sulfide copper deposition is activated conveniently, and meanwhile, the metal copper simple substance is produced through reduction.
And most of the solvent is removed from the slurry through spray drying, and meanwhile, the spray drying can also enable the material to form a double-gap structure, so that the specific surface area is increased, and a larger reaction area is formed. The treatment time of spray drying is short, so that the activity of the sulfide ions can be ensured, and the crystal structure can not be damaged.
And roasting the spray-dried material under the protection of inert gas. The roasting process can reduce CuS under a certain condition, partially convert the CuS into copper simple substance, and reduce copper sulfide acid dissolution reaction in the subsequent copper removal process.
Preferably, in step S1, the mass ratio of the activated carbon to the sulfation slag is 1: (4-5).
Preferably, in step S1, the ball milling process conditions are as follows: the ball material mass ratio is (5-8) to 1, the ball milling rotating speed is 300-500 r/min, and the ball milling time is 120-180 min.
During the ball milling process, stainless steel balls with diameters of 5mm and 3mm can be used. Optionally, the weight ratio of the stainless steel balls of 5mm and 3mm is 1:1.
Preferably, the average particle diameter of the sulfidation slag is 90-120 μm. Ball milling the vulcanized slag to 700-1000 meshes through ball milling treatment.
Preferably, in the step S2, the concentration of the sulfuric acid solution is 50-100 g/L.
Preferably, in the step S2, the mass ratio of the powder to the sulfuric acid solution is 0.8-1.2: 1.
preferably, in step S3, the spray drying conditions are as follows: the air inlet temperature is 150-200 ℃, the air outlet temperature is 60-100 ℃ and the time is 5-20 s.
Alternatively, the spray drying may be carried out using an atomizer (spray gun). In the spray drying process, the slurry is polymerized into mist particles through an atomizer, and is in direct contact with hot air for heat exchange, so that the drying of the slurry is completed in a short time.
Preferably, in step S4, the temperature of the baking treatment is 650-850 ℃ and the time is 60-90 min.
The invention also provides a copper removal method, which comprises the following steps:
adding the copper removing agent into a copper ion-containing solution, and stirring at 70-90 ℃ for 60-120 min to remove copper;
wherein, according to the concentration of copper ions in the solution, the addition amount of the copper removing agent is 1.0-1.3 times of the theoretical amount of reducing the copper ions in the solution.
Optionally, in the copper removal method, the stirring speed is 200-500 r/min.
The chemical reactions that occur primarily with copper ions include:
Cu 2+ +NiS＝CuS+Ni 2+ ；2Cu + +NiS＝Cu 2 S+Ni 2+ ；Cu 2+ +NiS 2 ＝CuS 2 +Ni 2+ 。
the copper ion-containing solution may be a leachate of a battery positive electrode material.
Optionally, the copper ion content in the copper-containing solution is 500-4000 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops a copper removing agent, a preparation method thereof and a copper removing method. The copper removing agent is prepared from the sulphurized slag generated in the recovery process of the waste batteries, has smaller particle diameter and larger specific surface area, has loose crystal structure and excellent activation performance, and is used for removing copper from the battery recovery leaching liquid and has excellent copper removal rate.
Drawings
FIG. 1 is an XRD pattern of the sulfidation slag used in example 1;
FIG. 2 is an SEM image of the sulfidation slag used in example 1;
FIG. 3 is an SEM image of the copper-removing agent of example 1;
FIG. 4 is a graph showing the copper removal rate change of the copper removing agent prepared in example 1 and the sulfidizing slag used in example 1 at different addition factors;
FIG. 5 is a graph showing the change in copper concentration of the copper scavenger prepared in example 1 at various addition factors.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings, but the examples are not intended to limit the present invention in any way.
The sulfidic slag adopted in the invention is taken from a wet smelting copper sulfide removal procedure, the average grain diameter is 98 mu m, wherein the copper content is 11.2%, and the nickel content is 54.6%.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a copper removing agent, which is prepared by the following steps:
s1, mixing active carbon with vulcanized slag according to a mass ratio of 1:5, ball milling treatment is carried out after mixing to obtain powder;
the ball milling treatment conditions are as follows: stainless steel balls with the diameters of 5mm and 3mm in a weight ratio of 1:1 are adopted, the ball material mass ratio is 6:1, the ball milling rotating speed is 400r/min, and the ball milling time is 150min;
s2, dispersing the powder obtained in the step S1 into a 60g/L sulfuric acid solution for pulping, wherein the mass ratio of the powder to the sulfuric acid solution is 1:1, obtaining slurry;
s3, carrying out spray drying on the slurry obtained in the step S2 to obtain a spray-dried material;
the spray drying conditions were: the air inlet temperature is 180 ℃, the air outlet temperature is 80 ℃ and the time is 10s;
s4, roasting the spray-dried material obtained in the step S3 under the protection of nitrogen, wherein the roasting temperature is 750 ℃ and the time is 70min, so as to obtain activated particles, namely the copper removing agent.
Example 2
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S1, the mass ratio of the active carbon to the vulcanized slag is 1:4, mixing.
Example 3
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S1, the mass ratio of the active carbon to the vulcanized slag is 1:2, mixing.
Example 4
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S1, the mass ratio of the active carbon to the vulcanized slag is 1:1, mixing.
Comparative example 1
This comparative example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S1, the mass ratio of the active carbon to the vulcanized slag is 1:7, mixing.
Comparative example 2
This comparative example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S1, the mass ratio of the active carbon to the vulcanized slag is 1: 0.5.
Example 5
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in step S1, the ball milling conditions are as follows: stainless steel balls with the diameters of 5mm and 3mm in a weight ratio of 1:1 are adopted, the ball mass ratio is 5:1, the ball milling rotating speed is 300r/min, and the ball milling time is 180min.
Example 6
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in step S1, the ball milling conditions are as follows: stainless steel balls with the diameters of 5mm and 3mm in a weight ratio of 1:1 are adopted, the ball mass ratio is 8:1, the ball milling rotating speed is 500r/min, and the ball milling time is 120min.
Example 7
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S2, the concentration of the sulfuric acid solution is 100g/L, and the mass ratio of the powder to the sulfuric acid solution is 0.8:1, a step of;
in step S3, the spray drying conditions are: the air inlet temperature is 150 ℃, the air outlet temperature is 60 ℃, and the time is 20s.
Example 8
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in step S3, the spray drying conditions are: the air inlet temperature is 200 ℃, the air outlet temperature is 100 ℃, and the time is 5s.
Example 9
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S4, the roasting temperature is 850 ℃ and the time is 60min.
Example 10
This example provides a copper scavenger, the preparation method differs from example 1 in that:
in the step S4, the roasting temperature is 650 ℃ and the roasting time is 90min.
The copper removing agents prepared in the embodiments 1 to 10 of the invention all have the following components: 62.5 to 71.3 percent of NiS and the NiS 2 5.5～10.3％，CuS 13.2～18.4％，Cu 2～4.5％，C 0.5～1.8％。
Comparative example 3
The comparative example provides a copper removing agent, and the preparation method is as follows:
s1, mixing active carbon with vulcanized slag according to a mass ratio of 1:5, dispersing the mixture into a 60g/L sulfuric acid solution for pulping, wherein the mass ratio of the powder to the sulfuric acid solution is 1:1, obtaining slurry;
s2, carrying out spray drying on the slurry obtained in the step S1 to obtain a spray-dried material;
the spray drying conditions were: the air inlet temperature is 180 ℃, the air outlet temperature is 80 ℃ and the time is 10s;
s3, roasting the spray-dried material obtained in the step S3 under the protection of nitrogen, wherein the roasting temperature is 750 ℃ and the time is 70min, and the copper removing agent is obtained.
Namely, the difference from example 1 is that the activated carbon was directly slurried without ball milling treatment after mixing with the sulfidizing slag.
Comparative example 4
The comparative example provides a copper removing agent, and the preparation method is as follows:
s1, mixing active carbon with vulcanized slag according to a mass ratio of 1:5, ball milling treatment is carried out after mixing to obtain powder;
the ball milling treatment conditions are as follows: stainless steel balls with the diameters of 5mm and 3mm in a weight ratio of 1:1 are adopted, the ball material mass ratio is 6:1, the ball milling rotating speed is 400r/min, and the ball milling time is 150min;
s2, dispersing the powder obtained in the step S1 into a 60g/L sulfuric acid solution for pulping, wherein the mass ratio of the powder to the sulfuric acid solution is 1:1, obtaining slurry;
s3, placing the slurry obtained in the step S2 in an oven, and drying at 180 ℃ for 2 hours to obtain a dried material;
s4, roasting the dried material obtained in the step S3 under the protection of nitrogen, wherein the roasting temperature is 750 ℃ and the time is 70min, and the copper removing agent is obtained.
I.e. differs from example 1 in that the spray drying of step S3 is replaced by a drying.
Performance testing
(1) XRD and/or SEM measurements of the sulphided slag used in example 1 and the copper scavenger produced, FIG. 1 is an XRD pattern of the sulphided slag used in example 1, an SEM pattern of the sulphided slag; FIG. 3 is an SEM image of the copper-removing agent of example 1.
It can be seen that the sulphidic slag contains copper sulphide and nickel sulphide. Compared with the sulfuration slag, the copper removing agent prepared by the preparation method disclosed by the invention has smaller particle size, larger specific surface area and looser crystal structure. The average grain diameter of the copper removing agent is 40-80 mu m, and the specific surface area is 320-500 m 2 /g。
(2) The copper removal performance of the copper removing agent obtained in the above examples and comparative examples is characterized, and specific test items, test methods and results are as follows:
taking the positive pole piece powder of a waste battery recovery enterprise in Hunan, wherein the main phase of the positive pole piece powder is LiCoO 2 H is adopted for the positive pole piece powder 2 SO 4 And H 2 O 2 Mixing and leaching, removing Fe and Al, and concentrating the leaching solution to obtain the final productTable 1 shows that the leachate contains Cu as an impurity in addition to Ni, co and Mn as main metals.
TABLE 1 Main Components of leachate (g/L)
(2.1) the copper removing agents prepared in examples 1 to 10 and comparative examples 1 to 4 were added to the leachate at a concentration of 4g/L, copper was removed, the reaction temperature was 85℃and the stirring speed was 300r/min, the reaction time was 90min, and the concentrations of the components in the leachate after copper removal were again detected.
Wherein, the copper removal agent prepared in example 1 is used for copper removal, and the concentration of each component in the leaching solution after copper removal is shown in Table 2.
TABLE 2 Main composition Table (g/L) of leachate after copper removal
It can be seen that the Cu content of the leaching solution is changed from 1600mg/L to 3.2mg/L after copper removal by using the copper removing agent of the embodiment 1, and the copper removal rate is 99.8%.
Copper removal rates of the copper scavengers of examples 1 to 10 and comparative examples 1 to 4 are shown in Table 3.
TABLE 3 copper removal Rate of copper scavengers of examples 1 to 10 and comparative examples 1 to 4
| Copper removal Rate (%) | Copper removal Rate (%) | ||
| Example 1 | 99.8 | Example 8 | 92.4 |
| Example 2 | 92.6 | Example 9 | 87.9 |
| Example 3 | 83.5 | Example 10 | 95.7 |
| Example 4 | 74.1 | Comparative example 1 | 52.4 |
| Example 5 | 89.4 | Comparative example 2 | 68.7 |
| Example 6 | 93.5 | Comparative example 3 | 72.4 |
| Example 7 | 89.6 | Comparative example 4 | 45.3 |
As can be seen from the test results in Table 3, the copper removal rate of the leachate by using the copper removing agent prepared in each example is high, and the copper removal rate of some examples reaches more than 90%.
According to examples 1 to 4 and comparative examples 1 and 2, the mass ratio of activated carbon to the sulfidation slag in step S1 has a large influence on the copper removal effect of the copper removing agent. When the mass ratio of the active carbon to the sulfation slag is 1: when the copper removal rate is within the range of (1) to (5), the copper removal rate is 74% or more, and the copper removal rates of example 1 and example 2 can be 90% or more. The copper removal rate of the copper removal agent tends to decrease as the content of the activated carbon increases relatively and the content of the sulfide slag decreases relatively. However, the inventors found that when the active carbon ratio is too low, the copper removal effect of the copper removing agent is greatly reduced, and the copper removal rate of comparative example 1 is only 52.4%. This is because the reduction effect of the copper-and nickel-containing sulfidation slag is affected by the insufficient firing reducing atmosphere caused by the too low proportion of activated carbon.
(2.2) adding the copper removing agent and the sulfide residues prepared in the embodiment 1 into the leaching solution respectively according to different addition factors, removing copper, stirring at a reaction temperature of 85 ℃ at a rotation speed of 300r/min for 90min, detecting the copper content in the leaching solution after copper removal again, and calculating the copper removal rate;
wherein, the addition multiple refers to: based on the concentration of copper ions in the leachate, the theoretical amount of copper scavenger required to reduce copper ions in the leachate is calculated, fold addition = actual addition/theoretical amount.
FIG. 4 is a graph showing the change in copper removal rates of the copper scavenger and the sulfidizing slag of example 1 at different addition factors; fig. 5 is a graph showing the change in copper concentration of the copper scavenger of example 1 at various addition factors.
It can be seen that the copper removal efficiency of the sulfidic slag is poor, and the copper removal rate is only 31.6% when the addition multiple is 1.3. The copper removing agent prepared by taking the sulfation slag as a raw material through the preparation method of the invention greatly improves the copper removing efficiency.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (13)
1. A copper removing agent is characterized by comprising NiS and NiS 2 And CuS.
2. The copper removal agent according to claim 1, comprising the following components in percentage by weight:
NiS62.5～71.3％，NiS 2 5.5～10.3％，CuS13.2～18.4％，Cu2～4.5％，C0.5～1.8％。
3. the copper scavenger according to claim 1, characterized in that the average particle size of the copper scavenger is 40-80 μm.
4. The copper-removing agent according to claim 1, wherein the specific surface area of the copper-removing agent is 320 to 500m 2 /g。
5. The method for producing a copper removing agent according to any one of claims 1 to 4, comprising the steps of:
s1, mixing active carbon with sulfide slag containing nickel and copper according to a mass ratio of 1: (1-5) mixing and then performing ball milling treatment to obtain powder;
s2, dispersing the powder obtained in the step S1 into sulfuric acid solution for pulping to obtain slurry;
s3, carrying out spray drying on the slurry obtained in the step S2 to obtain a spray-dried material;
s4, roasting the spray-dried material obtained in the step S3 under the protection of inert gas to obtain the copper removing agent.
6. The method for preparing a copper removing agent according to claim 5, wherein in the step S1, the mass ratio of the activated carbon to the sulfur slag containing nickel and copper is 1: (4-5).
7. The method for preparing a copper removing agent according to claim 5, wherein in the step S1, the ball milling process conditions are as follows: the ball material mass ratio is (5-8) to 1, the ball milling rotating speed is 300-500 r/min, and the ball milling time is 120-180 min.
8. The method for producing a copper removing agent according to claim 5, wherein in step S2, the concentration of the sulfuric acid solution is 50 to 100g/L.
9. The method for preparing copper removing agent according to claim 5, wherein in step S2, the mass ratio of the powder to sulfuric acid solution is 0.8-1.2: 1.
10. the method of producing a copper scavenger according to claim 5, wherein in step S3, the spray-drying conditions are: the air inlet temperature is 150-200 ℃, the air outlet temperature is 60-100 ℃ and the time is 5-20 s.
11. The method of producing a copper removing agent according to claim 5, wherein in step S4, the baking treatment is performed at a temperature of 650 to 850℃for 60 to 90 minutes.
12. The method for producing a copper removing agent according to claim 5, wherein the average particle diameter of the sulfidizing slag is 90 to 120. Mu.m.
13. A copper removal method, comprising the steps of:
adding a copper removing agent into the copper ion-containing solution, and stirring for 60-120 min at 70-90 ℃ to remove copper; wherein, according to the concentration of copper ions in the solution, the addition amount of the copper removing agent is 1.0-1.3 times of the theoretical amount of reducing the copper ions in the solution;
the copper scavenger is the copper scavenger according to any one of claims 1 to 4.
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| PCT/CN2023/079330 WO2024178723A1 (en) | 2023-03-02 | 2023-03-02 | Copper remover and preparation method therefor, and method for removing copper |
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| CN1032703C (en) * | 1994-06-29 | 1996-09-04 | 北京有色冶金设计研究总院 | Copper removing method for nickel electrolysis anolyte |
| CN101063210B (en) * | 2006-04-25 | 2010-05-26 | 襄樊化通化工有限责任公司 | Process for manufacturing highly active nickel cakes from recycled nickel-containing waste |
| JP5673471B2 (en) * | 2011-09-22 | 2015-02-18 | 住友金属鉱山株式会社 | Method for removing copper ions in aqueous nickel chloride solution and method for producing electronickel |
| CN108611493B (en) * | 2018-05-15 | 2020-01-07 | 湖南邦普循环科技有限公司 | Comprehensive recovery method of sulfide slag |
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