CN108034822B - A method of copper ion in removal tri compound sulfate liquor - Google Patents
A method of copper ion in removal tri compound sulfate liquor Download PDFInfo
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- CN108034822B CN108034822B CN201711276056.XA CN201711276056A CN108034822B CN 108034822 B CN108034822 B CN 108034822B CN 201711276056 A CN201711276056 A CN 201711276056A CN 108034822 B CN108034822 B CN 108034822B
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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
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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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
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The present invention relates to a kind of methods of copper ion in fine inorganic chemicals technical field more particularly to removal tri compound sulfate liquor, comprising the following steps: (1) tri compound sulfate liquor is put into electrolytic cell, is heated；(2) it using carbon plate as anode, is electrolysed by cathode of copper sheet；(3) in electrolytic process in sample detection solution copper content, when the content of copper be lower than 0.01ug/mL when stop be powered；(4) slag in anode plate and solution is filtered and washed, cleaning solution and filtrate are merged, obtains the tri compound sulfate liquor for removing copper ion；Wherein, the tri compound sulfate liquor is the mixed solution of cobaltous sulfate, nickel sulfate, manganese sulfate.
Description
Technical field
The present invention relates to copper in fine inorganic chemicals technical field more particularly to a kind of removal tri compound sulfate liquor
The method of ion.
Background technique
With the fast development of new-energy automobile industry, the continuous rapid growth of power lithium battery usage amount, in recent years
The learies of lithium battery are also in rapid growth.Compared to portable electronic devices such as mobile phone, notebooks, power lithium battery is scrapped
It measures huge.It containing valuable metals such as cobalt nickel manganese lithiums in lithium battery, while being also poisonous metal, if by lithium battery directly as discarded
Object is placed in environment, will cause seriously to pollute to soil environment and water environment.
The regeneration of valuable metal in lithium battery, not only contributes to the development of lithium battery industry, and can reduce ring
Border pollution problem.The recovery process of waste lithium cell mainly includes electric discharge, dismantling, crushes, sorting, alkali leaching, Ore Leaching, removes
Miscellaneous, extraction, back extraction, crystallization etc..Collector of the copper foil as cathode of lithium battery has part in dismantling and crushing process
Copper enters powder, then, is entered in solution by Ore Leaching process.
Currently, mainly there is the method for copper removal in tri compound sulfate liquor: addition NaHS generation copper sulfide precipitation,
Using the methods of N902 extractant extraction copper removal.But they have the loss of cobalt, nickel, manganese, Er Qiecui during copper removal
It is complex to remove process for copper, copper removal effect is extremely difficult to 100%, therefore, tri compound sulfate liquor remove impurity copper from
The method of son needs further to be studied.
Summary of the invention
In order to solve the defects of prior art, the present invention provides copper ions in a kind of removal tri compound sulfate liquor
Method.
A method of copper ion in removal tri compound sulfate liquor, comprising the following steps:
(1) tri compound sulfate liquor is put into electrolytic cell, is heated；
(2) it using carbon plate as anode, is electrolysed by cathode of copper sheet；
(3) in electrolytic process in sample detection solution copper content, stop when the content of copper is lower than 0.01ug/mL logical
Electricity；
(4) slag in anode plate and solution is filtered and washed, merges cleaning solution and filtrate to get the ternary of copper ion is removed
Sulfate composite salting liquid；
Wherein, the tri compound sulfate liquor is the mixed solution of cobaltous sulfate, nickel sulfate, manganese sulfate.
The method of copper ion in removal tri compound sulfate liquor above-mentioned, in step (1), the heating is by ternary
The temperature of sulfate composite salting liquid is heated to 20-100 DEG C.
The method of copper ion, described to be electrolysed in step (2) in removal tri compound sulfate liquor above-mentioned
When, control voltage is 2-3V, electric current 1.0-1.5A, current density 30-100A/m2。
It is above-mentioned removal tri compound sulfate liquor in copper ion method, the tri compound sulfate liquor it is dense
Degree is 150-200g/L.
The method of copper ion further includes preparation before the step (1) in removal tri compound sulfate liquor above-mentioned
The step of tri compound sulfate liquor:
1) the waste lithium cell pole piece of certain mass is weighed, is crushed；
2) strong base solution is added, stirring to no gas generates, filtering；
3) strong base solution of filter residue low concentration is beaten washing, filtering；
4) filter residue is added in dilution heat of sulfuric acid, is added with stirring hydrogen peroxide；
5) to fully reacting, filtering obtains tri compound sulfate liquor.
The method of copper ion, the waste lithium cell pole piece are positive plate in removal tri compound sulfate liquor above-mentioned
And negative electrode tab.
The method of copper ion, the highly basic are in NaOH, KOH, LiOH in removal tri compound sulfate liquor above-mentioned
One or more.
The method of copper ion, strong base solution concentration described in step 2) are in removal tri compound sulfate liquor above-mentioned
4-6mol/L, the concentration of strong base solution described in step 3) are 0.05-0.15mol/L.
The method of copper ion, the concentration of the dilute sulfuric acid are 1.5- in removal tri compound sulfate liquor above-mentioned
2.5mol/L。
The method of copper ion, the mass fraction of the hydrogen peroxide are 25- in removal tri compound sulfate liquor above-mentioned
30%.
It is had the advantages that using technical solution of the present invention
The present invention using the oxidation-reduction potential of metal ion difference, when being passed through direct current and being electrolysed, oxidisability
Stronger copper ion is reduced into elemental copper first on cathode and is precipitated, to remove from solution.The principle of the invention is simple, removes
The only loss of a small amount of metallic cobalt, nickel, manganese during copper, when content of copper ion is lower, electrolysis time is shorter, cobalt, nickel, manganese gold
It is also relatively small to belong to loss.
Moreover, because present invention utilizes electrochemical method, compared with common chemical method, the present invention without it is additional its
Its chemical reagent, not only saves energy, and avoids pollution of the added regent to environment, and therefore, the present invention is more in line with
Green Chemistry idea.
Specific embodiment
In order to fully understand the purpose of the present invention, feature and effect, by following specific embodiments, the present invention is made detailed
It describes in detail bright.For process of the invention in addition to following the description, remaining is all made of the conventional method or device of this field.Following nouns
Term is unless otherwise stated, all have the normally understood meaning of those skilled in the art.
The present invention provides copper ions in a kind of removal tri compound sulfate (cobaltous sulfate, nickel sulfate, manganese sulfate) solution
Method.Using electrolysis principle, oxidation reaction occurs for anode when electrolysis, and reduction reaction occurs for cathode, using carbon plate as anode, with copper
Plate is that cathode is electrolysed, and reduction reaction occurs on cathode and generates elemental copper for copper ion, thus molten from tri compound sulfate
It is removed in liquid.The present invention using various metal activities sequence (oxidation-reduction potential) difference, in electrolytic process oxidisability compared with
Strong copper ion is first precipitated from cathode, and removes from solution.
Specifically, the method for removing copper ion in tri compound sulfate liquor of the invention, includes the following steps:
(1) it is that 150-200g/L tri compound sulfate liquor is put into electrolytic cell by concentration, is heated to 20-100 DEG C,
Middle tri compound sulfate liquor is the mixed solution of cobaltous sulfate, nickel sulfate, manganese sulfate；
Wherein, being 20-100 DEG C for temperature setting can be improved reaction speed, shorten the reaction time.
(2) it using carbon plate as anode, is electrolysed by cathode of copper sheet, control voltage is 2-3V, electric current 1.0-1.5A, is led to
The area of coordination electrode plate in the solution is crossed, control current density is 30-100A/m2；
Using HB404 D.C. voltmeter and HB404 intelligent amperemeter, DC equipment is turned by exchange and obtains electricity needed for experiment
Pressure and electric current.
(3) in electrolytic process, at regular intervals in sample detection solution copper content, until the content of copper is lower than
Stop being powered when 0.01ug/mL；
(4) slag in anode plate and solution is filtered and washed, cleaning solution and filtrate are merged to get removing the three of copper ion
First sulfate composite salting liquid.
The main component for removing the tri compound sulfate mixture of copper ion is NiSO4、CoSO4、MnSO4, and it is a small amount of
Li2SO4、Na2SO4、CaSO4、MgSO4Deng.
Slag is collected, wash, weighs and analyze the quality of Ni, Co, Mn after drying, and then calculates tri compound sulfate
The loss amount of Ni, Co, Mn in mixture.
Wherein, before step (1), further include the steps that preparing tri compound sulfate liquor, specific as follows:
1) the waste lithium cell pole piece for weighing certain mass, is crushed using micromill；
Wherein, lithium battery pole slice includes positive plate and negative electrode tab, and positive plate collector is aluminium foil, and negative electrode tab collector is copper
Foil.
2) NaOH, KOH or LiOH solution of excessive 4-6mol/L is added, stirring to no gas generates, and filters；This step
Suddenly primarily to removing the aluminium in positive plate.The chemical reaction mainly occurred are as follows:
2Al+2OH-+2H2O=2AlO2 -+3H2↑
3) filter residue is washed twice with NaOH, KOH or LiOH solution mashing of 0.05-0.15mol/L, is obtained by filtration without aluminium
Filter residue；
4) filter residue is added in the dilution heat of sulfuric acid of 1.5-2.5mol/L, being added with stirring mass fraction is 25-30%
Hydrogen peroxide；The chemical equation to react are as follows:
2LiMO2+3H2SO4+H2O2=Li2SO4+2MSO4+4H2O+O2↑
M represents the mixture of Ni, Co, Mn.
5) to fully reacting, filtering discards filter residue to get tri compound sulfate liquor.
After being electrolysed 4~8h using method of the invention, the content of copper ion can be from tri compound sulfate liquor
2200ug/mL is down to 0.01ug/mL or less.
The principle of the invention is simple, can effectively remove the copper ion in tri compound sulfate liquor from solution,
Impurity copper, which is removed, for tri compound sulfate liquor provides a kind of new method.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
Embodiment 1
Waste lithium cell positive plate 300g is weighed at random, negative electrode tab 5g after being crushed with micromill, is slowly added into and contains
In the beaker for having the NaOH solution of 1.5L 5.0mol/L, stirring, until there is no gas generations.Filtering, with 0.1mol/L's
NaOH solution is washed twice by solid-to-liquid ratio 1:3 mashing.Powder after washing is slowly added into the sulfuric acid containing 1.75L 2mol/L
The hydrogen peroxide that about 250mL mass fraction is 30% is slowly added in the beaker of solution, under stirring.After reacting 2h, body is obtained by filtration
Product is the tri compound sulfate liquor of 2L, and the concentration for being detected wherein each ingredient is NiSO4: 60.79g/L, CoSO4:
63.24g/L MnSO4: 64.38g/L, Cu2+Content is 2181ug/mL.Water in electrolytic cell is heated to 95 DEG C or so, with carbon plate
For anode, be electrolysed by cathode of copper sheet, control 2.7 ± 0.2V of voltage, 1.2 ± 0.1A of electric current, and by control solution with
The contact area of pole plate makes current density control in 90A/m2Left and right.Copper contains in separately sampled survey solution when being electrolysed 2h, 5h and 8h
Amount is respectively 1295ug/mL, 149ug/mL and 0 (ICP is not detected).
After electrolysis, the slag in solution Anodic and solution is collected, wash, weighs and analyzes after drying, wherein slag
In containing Ni, Co, Mn be respectively 2.62g, 0.88g, 5.13g, loss amount is respectively 5.68%, 1.83%, 10.95%.
Below by taking nickel as an example, the calculation method of metal loss amount is as follows:
The volume of tri compound sulfate is 2L, and the concentration of nickel sulfate is 60.79g/L,
Then: mNiSO4=2L × 60.79g/L=121.58g
mNi=nNi×MNi=nNiSO4×MNi=(mNiSO4÷M NiSO4)×MNi
=(121.58g ÷ 154.69g/mol) × 58.69g/mol
=46.13g
The loss amount of nickel=(2.62 ÷ 46.13) × 100%=5.68%
In kind calculate the loss amount of Co, Mn.
Embodiment 2
Waste lithium cell positive plate 300g, negative electrode tab 3g are weighed at random, after being crushed with micromill, is slowly added into Sheng
In the beaker for having the NaOH solution of 1.5L 5.0mol/L, stirring is lower until there is no gas generations.Filtering, and use 0.1mol/L
NaOH solution by solid-to-liquid ratio 1:3 mashing wash twice.Powder after washing, which is slowly added into, fills about 1.75L 2mol/L's
In the beaker of sulfuric acid solution, stirring, be slowly added to about 250mL mass fraction be 30% hydrogen peroxide, react 2h after, filter three
First sulfate composite salting liquid 2L, the concentration for being detected wherein each ingredient is NiSO4: 59.44g/L, CoSO4: 43.76g/L,
MnSO4: 70.61g/L, wherein Cu2+Content is 1367ug/mL.Heating water bath is to 60 DEG C in electrolytic cell, using carbon plate as anode, with
Copper sheet is that cathode is electrolysed, and controls 2.5 ± 0.2V of voltage, 1.3 ± 0.1A of electric current, and the contact by control solution with pole plate
Area makes current density 60A/m2Left and right.The separately sampled copper content surveyed in solution when being electrolysed 2h, 4h and 6h, respectively
591ug/mL, 86ug/mL and 0.004ug/mL.After electrolysis, the slag in solution Anodic and solution is collected into washing drying
After weigh and analyze, containing Ni, Co, Mn be respectively 1.37g, 0.39g, 2.37g in slag, loss amount is respectively 3.04%,
1.17%, 4.61%.
Embodiment 3
Waste lithium cell positive plate 250g is weighed at random, negative electrode tab 0.3g after being crushed with micromill, is slowly added into
In the beaker for filling the NaOH solution of 1.5L 5.0mol/L, stirring, until there is no gas generations.0.1mol/L is used after filtering
NaOH solution by solid-to-liquid ratio 1:3 mashing wash twice.Powder after washing is slowly added into the sulphur for filling 1.8L 1.5mol/L
In the beaker of acid solution, stirring is slowly added to the hydrogen peroxide that about 200mL mass fraction is 30%, after reacting 2h, filters to obtain ternary
Sulfate composite salting liquid 2L, the concentration for being detected wherein each ingredient is NiSO4: 78.35g/L, CoSO4: 33.59g/L, MnSO4:
52.18g/L wherein Cu2+Content is 120ug/mL.Using carbon plate as anode in electrolytic cell, electricity is carried out at room temperature by cathode of copper sheet
Solution controls 2.0 ± 0.2V of voltage, 1.0 ± 0.1A of electric current, and by the contact area of control solution and pole plate, makes current density
Control is in 35A/m2Left and right.Being electrolysed copper content in the separately sampled survey solution of 2h, 4h is respectively 36ug/mL and 0 (ICP is not detected).
After electrolysis, weighs and analyze after the slag in solution Anodic and solution is collected washing drying, containing Ni, Co, Mn points in slag
Not Wei 1.56g, 0.23g, 1.53g, loss amount is respectively 2.62%, 0.90%, 4.03%.
Embodiment 4
Waste lithium cell positive plate 250g, negative electrode tab 3g are weighed at random, after being crushed with micromill, is slowly added into Sheng
In the beaker for having the NaOH solution of 1.5L 4.0mol/L, stirring, until there is no gas generations.With 0.15mol/L's after filtering
NaOH solution is washed twice by solid-to-liquid ratio 1:3 mashing.Powder after washing is slowly added into the sulfuric acid for filling 1.8L 1.5mol/L
In the beaker of solution, stirring is slowly added to the hydrogen peroxide that about 200mL mass fraction is 25%, after reacting 2h, filter ternary is multiple
Sulfate liquor 2L is closed, the concentration for being detected wherein each ingredient is NiSO4: 77.96g/L, CoSO4: 34.65g/L, MnSO4:
49.99g/L wherein Cu2+Content is 1310ug/mL.Using carbon plate as anode in electrolytic cell, using copper sheet as water-bath in cathode electrolytic cell
60 DEG C are heated to, 2.5 ± 0.2V of voltage, 1.3 ± 0.1A of electric current are controlled, and by the contact area of control solution and pole plate, is made
Current density is controlled in 70A/m2Left and right.Electrolysis the separately sampled survey solution of 2h, 4h, 6h in copper content be respectively 459ug/mL,
23ug/mL and 0 (ICP is not detected).After electrolysis, weigh simultaneously after the slag in solution Anodic and solution is collected washing drying
Analysis containing Ni, Co, Mn is respectively 1.49g, 0.46g, 1.21g in slag, loss amount is respectively 2.51%, 1.74%,
3.32%.
Embodiment 5
Waste lithium cell positive plate 250g, negative electrode tab 3g are weighed at random, after being crushed with micromill, is slowly added into Sheng
In the beaker for having the NaOH solution of 1.5L 6.0mol/L, stirring, until there is no gas generations.With 0.05mol/L's after filtering
NaOH solution is washed twice by solid-to-liquid ratio 1:3 mashing.Powder after washing is slowly added into the sulfuric acid for filling 1.8L 1.5mol/L
In the beaker of solution, stirring is slowly added to the hydrogen peroxide that about 200mL mass fraction is 30%, after reacting 2h, filter ternary is multiple
Sulfate liquor 2L is closed, the concentration for being detected wherein each ingredient is NiSO4: 76.94g/L, CoSO4: 33.64g/L, MnSO4:
53.29g/L wherein Cu2+Content is 1261ug/mL.Using carbon plate as anode in electrolytic cell, electricity is carried out at room temperature by cathode of copper sheet
Solution controls 2.0 ± 0.2V of voltage, 1.0 ± 0.1A of electric current, and by the contact area of control solution and pole plate, makes current density
Control is in 45A/m2Left and right.Being electrolysed copper content in the separately sampled survey solution of 2h, 4h, 6h, 8h is respectively 713ug/mL, 156ug/
ML, 21ug/mL and 0.005ug/mL.After electrolysis, weigh after the slag in solution Anodic and solution is collected washing drying
And analyze, containing Ni, Co, Mn be respectively 1.38g, 0.22g, 1.35g in slag, loss amount is respectively 2.43%, 0.86%,
3.48%.
The present invention is hereinbefore disclosed with preferred embodiment, but it should be understood by those skilled in the art that, these
Embodiment is only used for describing the present invention, but should not be understood as limiting the scope of the invention.It should be noted that all implement with these
Example equivalent variation and displacement, should all be set as being covered by scope of the presently claimed invention.Therefore, protection scope of the present invention
It should be subject to range defined in claims.
Claims (8)
1. a kind of method of copper ion in removal tri compound sulfate liquor, which comprises the following steps:
(1) tri compound sulfate liquor is put into electrolytic cell, is heated；
(2) it using carbon plate as anode, is electrolysed by cathode of copper sheet；
(3) in electrolytic process in sample detection solution copper content, when the content of copper be lower than 0.01ug/mL when stop be powered；
(4) slag in anode plate and solution is filtered and washed, merges cleaning solution and filtrate to get the tri compound of copper ion is removed
Sulfate liquor；
Wherein, the tri compound sulfate liquor is the mixed solution of cobaltous sulfate, nickel sulfate, manganese sulfate；
Wherein, the concentration of the tri compound sulfate liquor is 150-200g/L；
Wherein, described when being electrolysed in step (2), control voltage is 2-3V, electric current 1.0-1.5A, and current density is
35-70A/m2。
2. the method for copper ion in removal tri compound sulfate liquor according to claim 1, which is characterized in that step
(1) in, the heating is that the temperature of tri compound sulfate liquor is heated to 20-100 DEG C.
3. the method for copper ion in removal tri compound sulfate liquor according to claim 1 or 2, which is characterized in that
Before the step (1), further include the steps that preparing tri compound sulfate liquor:
1) the waste lithium cell pole piece of certain mass is weighed, is crushed；
2) strong base solution is added, stirring to no gas generates, filtering；
3) strong base solution of filter residue low concentration is beaten washing, filtering；
4) filter residue is added in dilution heat of sulfuric acid, is added with stirring hydrogen peroxide；
5) to fully reacting, filtering obtains tri compound sulfate liquor.
4. the method for copper ion in removal tri compound sulfate liquor according to claim 3, which is characterized in that described
Waste lithium cell pole piece is positive plate and negative electrode tab.
5. the method for copper ion in removal tri compound sulfate liquor according to claim 3, which is characterized in that described
Highly basic is one or more of NaOH, KOH, LiOH.
6. the method for copper ion in removal tri compound sulfate liquor according to claim 3, which is characterized in that step
2) strong base solution concentration described in is 4-6mol/L, and the concentration of strong base solution described in step 3) is 0.05-0.15mol/L.
7. the method for copper ion in removal tri compound sulfate liquor according to claim 3, which is characterized in that described
The concentration of dilute sulfuric acid is 1.5-2.5mol/L.
8. the method for copper ion in removal tri compound sulfate liquor according to claim 3, which is characterized in that described
The mass fraction of hydrogen peroxide is 25-30%.
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| CN101575715A (en) * | 2009-06-22 | 2009-11-11 | 中南大学 | Method for extracting valuable metals from electronic waste |
| CN104131316A (en) * | 2014-07-04 | 2014-11-05 | 中南大学 | Electrolysis method for separating copper from cobalt and nickel in chloride ion ammoniacal system and application of products thereof |
| CN105789724A (en) * | 2014-12-24 | 2016-07-20 | 中国电子工程设计院 | Treatment method for waste lithium-ion battery |
| CN107117661A (en) * | 2017-05-26 | 2017-09-01 | 金川集团股份有限公司 | The method that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery reclaimed using liquid phase method |
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