CN109735709A - A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material - Google Patents
A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material Download PDFInfo
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Abstract
The invention discloses a kind of methods removing calcium and magnesium slag recycling lithium and prepare ternary precursor material, belong to waste and old lithium ion battery hydrometallurgic recovery field, the following steps are included: (1) magnesium salts makes the transition, (2) heavy cobalt nickel manganese, (3) alkalization demagging, (4) lithium carbonate is prepared, (5) acidleach nickel cobalt manganese slag, (6) removing calcium and magnesium, (7) it extracts, (8) presoma is synthesized, (9), which are dried, is made ternary precursor material；Present invention process is simple, low energy consumption, safety and stability, the separative efficiency of cobalt nickel manganese and lithium is high in the process, and each valuable metal comprehensive recovery is high, the main content of lithium carbonate prepared by the present invention is up to 99.61%, reach LITHIUM BATTERY requirement, wherein nickel cobalt manganese lithium overall recovery is up to 98.5% in removing calcium and magnesium slag, and the lithium rate of recovery is up to 98.8%, and the present invention is easy to industrialized production, has high economic benefit.
Description
Technical field
The present invention relates to waste lithium cell hydrometallurgic recovery field, before especially a kind of removing calcium and magnesium slag recycling lithium and preparation ternary
The method for driving body material.
Background technique
Lithium battery is extensive because of the advantages that it is high with energy density, and open-circuit voltage is high, and charge/discharge speed is fast, and the service life is long
For mobile phone, computer, the digital products such as camera.As China greatly develops new-energy automobile industry, in recent years, lithium battery industry
Explosive growth is presented.It is shown according to GGII investigational data, Chinese power battery yield 44.5GWh, Zhan Quanqiu total amount in 2017
50% or more, China has become global maximum lithium battery production and consumption market.
For lithium battery after nearly thousand charge and discharge cycles, internal work ion will gradually loss of activity.Lithium battery day
Widely application will certainly generate a large amount of old and useless battery to benefit.If arbitrarily abandoning and not only bringing threat to environment, and cause gold
Belong to the waste of resource, therefore the recycling of waste lithium cell is had a very important significance.
Waste lithium cell recovery process is divided into front end pretreatment and rear end chemical recovery.And current waste lithium cell rear end
It learns and recycles mainly based on wet process.By taking ternary material battery as an example, wet recycling process is taken extensively: reduction acidleach-purification removes
Miscellaneous-extraction and separation technology process.In purification and impurity removal process, key is to remove calcium, magnesium addition in leachate.Patent
CN106505225A removes calcium, magnesium in the form of the calcirm-fluoride and magnesium fluoride of property hard to tolerate by the way that soluble fluoride salt dissolving is added.But
Since the fluoride of cobalt, nickel, manganese, lithium belongs to microsolubility substance, a large amount of nickel cobalt manganese gold certainly will be had while removing calcium and magnesium
Category is precipitated out in the form of fluoride.Containing a large amount of valuable metal nickel, cobalt, manganese, lithium etc. in such removing calcium and magnesium slag, and in text
The recycling for having related only to lithium greatly reduces the rate of recovery of valuable metal.This patent is while recycling lithium prepares lithium carbonate
It has further recycled valuable metal nickel, cobalt, manganese and has prepared ternary precursor material, realized the comprehensive utilization of resource, and the present invention
Nickel cobalt manganese the rate of recovery 98% or more, lithium is recovered as 96% or more.
Summary of the invention
To solve the above problems, lithium is recycled the invention discloses a kind of removing calcium and magnesium slag and prepare ternary precursor
The method of material, includes the following steps:
(1) magnesium salts makes the transition, and slurries are made in the magnesium salts that removing calcium and magnesium slag and magnesium ion concentration are 30-100g/L, are added inorganic
Acid, regulation system pH are 1.0-5.0, heating stirring 1-5h, and filtering obtains transition liquid and is fluorinated calcium and magnesium slag；
(2) it sinks cobalt nickel manganese, precipitating reagent is added in the transition liquid in step (1), control system temperature is 25-100 DEG C, will
The form and Separation of Li and Mg that cobalt nickel manganese in transition liquid is precipitated with hydroxide nickel cobalt manganese, obtain nickel cobalt manganese slag and crude lithium liquid；
(3) acidleach nickel cobalt manganese slag, by step (2) nickel cobalt manganese slag and tap water size mixing, control liquid consolidate mass ratio as 2-
Slurry is made in 5:1, and inorganic acid is added into slurry, and adjusting pH is 0-5, is stirred to react 0.5-1h, obtains pickle liquor and acidleach
Slag；
(4) soluble fluoride salt dissolving, control system temperature 50-100 removing calcium and magnesium: are added in the pickle liquor obtained to step (3)
DEG C, it is filtered after being stirred to react 0.5-2h, obtains deliming magnesium liquid and removing calcium and magnesium slag；
(5) it extracts: obtaining the manganese of nickel containing cobalt with the metallic cobalt nickel manganese in organic extractant removing calcium with solvent extraction magnesium liquid, then through back extraction
Strip liquor；
(6) it synthesizes presoma: into the strip liquor of step (5) with addition of cobalt nickel manganese soluble-salt, sodium hydroxide and ammonia is added
Water, control system pH to 9-12, keeping reaction temperature is that 60-70 DEG C of stirring 1-5h obtains ball-shape nickel hydroxide cobalt manganese；
(7) dry: ball-shape nickel hydroxide cobalt manganese described in step (6) obtains ternary through 100-500 DEG C of high temperature drying 2-5h
Persursor material.
According to the above scheme, cobalt in removing calcium and magnesium slag described in step (1), nickel, manganese, lithium mass percent be respectively 1-
10%.
As a preferred solution of the present invention, including at least one following technical characteristic:
It is 2-5:1 that the removing calcium and magnesium slag and the liquid of magnesium salts slurrying, which consolidate mass ratio,；
The temperature of the heating stirring is 50-100 DEG C；
The stirring rate of the heating stirring are as follows: 100-400rpm/s；
The magnesium salts is at least one of magnesium sulfate, magnesium nitrate, magnesium chloride；
The additional amount of the magnesium salts is that cobalt, nickel, manganese, lithium are wholly converted into soluble-salt by chemical reaction in fluorination calcium and magnesium slag
1.1-2.0 times of theoretical quality needed for equation calculates.
As a preferred solution of the present invention, in step (2), the precipitating reagent is sodium hydroxide, in potassium hydroxide, ammonium hydroxide
It is at least one；The additional amount of the precipitating reagent is that cobalt, nickel, manganese are wholly converted into hydroxide by chemical reaction equation in transition liquid
1.0-2.0 times of theoretical quality needed for formula calculates.
As a preferred solution of the present invention, the inorganic acid in step (1) and (3) be sulfuric acid, nitric acid, in hydrochloric acid extremely
Few one kind.
As a preferred solution of the present invention, include at least one following technical characteristic in step (4):
The soluble fluoride salt dissolving is at least one of sodium fluoride, ammonium fluoride；
Control reaction system pH is 0-5；
Stirring rate is 100-400rpm/s.
As a preferred solution of the present invention, the deliming magnesium liquid pH value in the step (5) is 3.0-6.0, organic extraction
Taking agent is the organic mixture of P507, sulfonated kerosene, volume ratio 1:1-5, saponification degree 40%-70%.
It as a preferred solution of the present invention, is 8:1:1 or 6:2:2 or 5:2:3 by nickel cobalt manganese molar ratio in the step (6)
Cobalt nickel mn sulphate needed for supplying prepares ternary precursor material, and the ternary precursor material is Ni0.8Co0.1Mn0.1
(OH)2Type or Ni0.6Co0.2Mn0.2(OH)2Type or Ni0.5Co0.2Mn0.3(OH)2Type.
As a preferred solution of the present invention, further comprising the steps of:
S1: the agent of alkali formula is added in the crude lithium liquid in step (2) for alkalization demagging, adjusts solution ph to 10.0-
13.0, filtering obtains purification lithium liquid and magnesium hydroxide slag；
S2: preparing lithium carbonate, and sodium carbonate liquor is added in the purification lithium liquid into step S1, makes lithium in the form of lithium carbonate
It is precipitated out, battery-level lithium carbonate is made after washed, drying.
As a preferred solution of the present invention, in the step S1 alkali formula agent be sodium hydroxide, potassium hydroxide, lithium hydroxide,
At least one of ammonium hydroxide.
Working principle: reaction equation involved in the step (1) are as follows:
CoF2+Mg2+→MgF2↓+Co2+；
NiF2+Mg2+→MgF2↓+Ni2+；
MnF2+Mg2+→MgF2↓+Mn2+；
LiF+Mg2+→MgF2↓+Li+
Reaction equation involved in the step (2) are as follows:
2OH-+Co2+=Co (OH)2↓；
2OH-+Ni2+=Ni (OH)2↓
2OH-+Mn2+=Mn (OH)2↓
Reaction equation involved in the step (3) are as follows:
Mn(OH)2+2H2+=Mn2++2H2O
Co(OH)2+2H2+=Co2++2H2O
Ni(OH)2+2H2+=Ni2++2H2O
Reaction equation involved in the step (4) are as follows:
Mg2++2F-=MgF2↓
Ca2++2F-=CaF2↓
Reaction equation involved in the step (6) are as follows:
Co2++OH-=Co (OH)2↓
Ni2++OH-=Ni (OH)2↓
Mn2++OH-=Mn (OH)2↓
Reaction equation involved in the step S1 are as follows:
2OH-+Mg2+=Mg (OH)2↓
Reaction equation involved in the step S2 are as follows:
2Li++CO3 2-=Li2CO3↓
The invention has the advantages that:
(1) present invention is to carry out magnesium to removing calcium and magnesium slag first using waste lithium cell leachate removing calcium and magnesium slag as recycle object
Salt transition, obtains nickel cobalt manganese lithium solution, and by heavy nickel cobalt manganese, acidleach, removing calcium and magnesium extracts, obtains spherical shape using synthetic reaction
The ternary precursor material of nickel cobalt manganese corresponding mol ratio is prepared in hydroxide nickel cobalt manganese, drying.It is crude after its heavy nickel cobalt manganese
Lithium liquid is successively added the agent of alkali formula and separates the lithium in crude lithium liquid with magnesium, and the purification lithium liquid after alkalization can prepare LITHIUM BATTERY
Lithium carbonate.
(2) the method for the present invention simple process, low energy consumption, safety and stability, and the separative efficiency of cobalt nickel manganese and lithium is high in the process, and
The content of nickel cobalt is 100ppm hereinafter, the content of lithium is 0.1% hereinafter, each valuable metal is comprehensive in nickel cobalt manganese slag in crude lithium liquid
The rate of recovery is high, and the yield of nickel cobalt manganese is 95% or more；Lithium transition yield is 95% or more.The lithium carbonate purity of preparation is up to
99.61%, quality is good, can reach battery-level lithium carbonate standard.
(3) traditional lithium fluoride and removing calcium and magnesium slag recycling lithium are not directed to the recycling of valuable metal nickel cobalt, feature of the present invention
It is by introducing heavy nickel cobalt process, to realize the separation of nickel, cobalt and lithium, reach the comprehensive reutilization of resource and have
The rate of recovery of valence metal is up to 95% or more.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Fig. 1 in reference to the accompanying drawing recycles lithium to one of present invention removing calcium and magnesium slag and prepares ternary precursor material
Method be further described.
A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material, with reference to Fig. 1, process flow is as follows:
(1) magnesium salts makes the transition, and slurries are made in the magnesium salts that removing calcium and magnesium slag and magnesium ion concentration are 30-100g/L, are added inorganic
Acid, regulation system pH are 1.0-5.0, heating stirring 1-5h, and filtering obtains transition liquid and is fluorinated calcium and magnesium slag；
It is 2-5:1 that the removing calcium and magnesium slag and the liquid of magnesium salts slurrying, which consolidate mass ratio,；
The temperature of the heating stirring is 50-100 DEG C；
The stirring rate of the heating stirring are as follows: 100-400rpm/s；
The magnesium salts is at least one of magnesium sulfate, magnesium nitrate, magnesium chloride；
The additional amount of the magnesium salts is that cobalt, nickel, manganese, lithium are wholly converted into soluble-salt by chemical reaction in fluorination calcium and magnesium slag
1.1-2.0 times of theoretical quality needed for equation calculates.
(2) it sinks cobalt nickel manganese, precipitating reagent is added in the transition liquid in step (1), control system temperature is 25-100 DEG C, will
The form and Separation of Li and Mg that cobalt nickel manganese in transition liquid is precipitated with hydroxide nickel cobalt manganese, obtain nickel cobalt manganese slag and crude lithium liquid.
The precipitating reagent is at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide；The additional amount of the precipitating reagent is to turn
Cobalt, nickel, manganese are wholly converted into the 1.0-2.0 of theoretical quality needed for hydroxide is calculated by chemical equation in type liquid
Times.
(3) acidleach nickel cobalt manganese slag, by step (2) nickel cobalt manganese slag and tap water size mixing, control liquid consolidate mass ratio as 2-
Slurry is made in 5:1, and inorganic acid is added into slurry, and adjusting pH is 0-5, is stirred to react 0.5-1h, obtains pickle liquor and acidleach
Slag；
(4) soluble fluoride salt dissolving, control system temperature 50-100 removing calcium and magnesium: are added in the pickle liquor obtained to step (3)
DEG C, system pH is 0-5, filters after being stirred to react 0.5-2h, obtains deliming magnesium liquid and removing calcium and magnesium slag；
The soluble fluoride salt dissolving is at least one of sodium fluoride, ammonium fluoride；
Stirring rate is 100-400rpm/s.
(5) it extracts: obtaining the manganese of nickel containing cobalt with the metallic cobalt nickel manganese in organic extractant removing calcium with solvent extraction magnesium liquid, then through back extraction
Strip liquor；Deliming magnesium liquid pH value in this step is 3.0-6.0, and the organic extractant is P507, the organic of sulfonated kerosene mixes
Close object, volume ratio 1:1-5, saponification degree 40%-70%.
(6) it synthesizes presoma: into the strip liquor of step (5) with addition of cobalt nickel manganese soluble-salt, sodium hydroxide and ammonia is added
Water, control system pH to 9-12, keeping reaction temperature is that 60-70 DEG C of stirring 1-5h obtains ball-shape nickel hydroxide cobalt manganese；
(7) dry: ball-shape nickel hydroxide cobalt manganese described in step (6) obtains ternary through 100-500 DEG C of high temperature drying 2-5h
Persursor material.
According to the above scheme, cobalt in removing calcium and magnesium slag described in step (1), nickel, manganese, lithium mass percent be respectively 1-
10%.
The inorganic acid of the step (1) and (3) is at least one of sulfuric acid, nitric acid, hydrochloric acid.
It as a preferred solution of the present invention, is 8:1:1 or 6:2:2 or 5:2:3 by nickel cobalt manganese molar ratio in the step (6)
Cobalt nickel mn sulphate needed for supplying prepares ternary precursor material, and the ternary precursor material is Ni0.8Co0.1Mn0.1
(OH)2Type or Ni0.6Co0.2Mn0.2(OH)2Type or Ni0.5Co0.2Mn0.3(OH)2Type.
As a preferred solution of the present invention, further comprising the steps of:
S1: the agent of alkali formula is added in the crude lithium liquid in step (2) for alkalization demagging, adjusts solution ph to 10.0-
13.0, filtering obtains purification lithium liquid and magnesium hydroxide slag；
S2: preparing lithium carbonate, and sodium carbonate liquor is added in the purification lithium liquid into step S1, makes lithium in the form of lithium carbonate
It is precipitated out, battery-level lithium carbonate is made after washed, drying.
As a preferred solution of the present invention, in the step S1 alkali formula agent be sodium hydroxide, potassium hydroxide, lithium hydroxide,
At least one of ammonium hydroxide.
Embodiment 1
(1) magnesium salts makes the transition: removing calcium and magnesium slag 200kg and 0.54m3Magnesium ion concentration is that slurry is made in 77g/L magnesium chloride solution
Liquid, the additional amount of magnesium salts are cobalt, nickel, manganese, lithium all leach required theoretical quality in calcium and magnesium slag 1.1 times, then use 20L salt
The pH value of system is adjusted to 3.0 by acid.Heating is opened, keeps system temperature to filter after 95 DEG C of stirring 1h, stirring rate is
200rpm/s obtains 0.52m3Make the transition liquid.It is as follows that transition liquid Principle components analysis the results are shown in Table 1:
The transition liquid Principle components analysis result of table 1
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 12.80 | 29.03 | 15.06 | 28.5 | 3.2 | 13 | 0.001 | 0.002 |
(2) heavy nickel cobalt manganese: 0.52m obtained above is pressed3Cobalt, nickel, manganese are wholly converted into hydroxide nickel cobalt manganese in transition liquid
1.1 times of addition sodium hydroxide 45kg of theoretical quality needed for calculating by chemical equation, make cobalt, nickel, manganese with hydroxide
The form of object is separated with lithium, magnesium.It is filtered after replacement stirring 0.5h, obtains 0.46m3Crude lithium liquid and 130kg nickel cobalt manganese slag.Crude lithium
It is as follows that liquid Principle components analysis the results are shown in Table 2:
The crude lithium liquid Principle components analysis result of table 2
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.01 | 0.05 | 0.08 | 32.19 | 2.9 | 13.2 | 0.001 | 0.002 |
(3) heavy nickel cobalt manganese slag and 0.4m in 130kg step (2) acidleach: are added into reaction kettle3Tap water slurry is made
Liquid, it is 1.0 that slurry pH, which is adjusted to pH, with 51kg concentrated hydrochloric acid.0.5h filtering is stirred, 0.42m is obtained3Pickle liquor.
(4) removing calcium and magnesium: 17.8kg sodium fluoride is added in the pickle liquor obtained to step (3), 90 DEG C of control system temperature are stirred
It is filtered after mixing reaction 2h, stirring rate 300rpm/s obtains 0.4m3Deliming magnesium liquid.Calcium content is in deliming magnesium liquid after measured
0.0002g/L, content of magnesium 0.0005g/L.
(5) it extracts: the deliming magnesium liquid pH value in step (4) is adjusted to 3.0, P507/ sulfonated kerosene (volume ratio 1:3),
The organic extractant that saponification degree is 65% is extracted through 8 stage countercurrents, obtains strip liquor 0.32m after 5 grades of back extraction3, wherein the knot of each ingredient
Fruit is shown in Table 4.
Principle components analysis result in 4 strip liquor of table
| Element | Co | Ni | Mn | Ca | Mg | Fe | Al |
| Content/(g/L) | 20.38 | 45.99 | 23.49 | 0.001 | 0.0015 | It is not detected | 0.0002 |
(6) it synthesizes presoma: being 5:2:3 by the nickel of design, cobalt, manganese molar ratio.To in step (7) with addition of sulphur in strip liquor
Sour nickel and manganese sulfate.Sodium hydroxide and ammonium hydroxide are added into reaction kettle, control system pH to 11.5, keeping reaction temperature is 65 DEG C
Stirring 4h obtains ball-shape nickel hydroxide cobalt manganese.
(7) it dries: ball-shape nickel hydroxide cobalt manganese manufactured in the present embodiment is obtained through 150 DEG C of high temperature drying 5h
Ni0.5Co0.2Mn0.3(OH)2Type ternary precursor 51.02Kg, is 97% from the overall recovery for being recovered to finished product nickel cobalt manganese.
The wherein rate of recovery of cobalt are as follows: 98.0%；The rate of recovery of nickel are as follows: 97.5%；The rate of recovery of manganese are as follows: 96.0%.
Embodiment 2
The present embodiment is to be further optimized on the basis of embodiment 1, specifically:
S1: alkalization demagging: to 0.46m obtained in step (2)30.1m is added in crude lithium liquid332wt% sodium hydroxide
Solution adjusts solution ph to 12.0.1h filtering is stirred, 0.52m is obtained3Refine lithium liquid.Refine lithium liquid Principle components analysis result
It is as follows to be shown in Table 3:
Table 3 refines lithium liquid Principle components analysis result
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.0001 | It is not detected | 0.0005 | 28.47 | 0.12 | 0.0001 | 0.0005 | 0.0002 |
S2: it prepares lithium carbonate: purification lithium liquid being warming up to 95 DEG C, is then slowly added into the sodium carbonate liquor of 300g/L
0.37m3, stirring 0.5h filtering, stirring rate 250rpm/s.Filter residue is washed again, drying obtains the production of 75.77kg lithium carbonate
Product.Lithium carbonate product technical indicator is shown in Table 13,14 in the present embodiment.
Embodiment 3
(1) magnesium salts makes the transition: removing calcium and magnesium slag 200kg and 0.6m3Magnesium ion concentration is that slurry is made in 61g/L Adlerika
Liquid, the additional amount of magnesium salts are cobalt, nickel, manganese, lithium all leach required theoretical amount in calcium and magnesium slag 1.2 times, then use the dense sulphur of 20L
The pH value of system is adjusted to 1.0 by acid.Heating is opened, keeps system temperature to filter after 95 DEG C of stirring 1h, stirring rate is
200rpm/s obtains 0.63m3Make the transition liquid.It is as follows that transition liquid Principle components analysis the results are shown in Table 5:
The transition liquid Principle components analysis result of table 5
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 6.3 | 14.6 | 3.2 | 22.1 | 1.1 | 8.5 | 0.002 | 0.001 |
(2) precipitate cobalt nickel manganese: the 0.63m of step (1) is pressed3Cobalt, nickel, manganese are wholly converted into hydroxide nickel cobalt manganese in transition liquid
1.1 times of addition sodium hydroxide 23kg of theoretical amount needed for calculating by chemical equation, make cobalt, nickel, manganese with hydroxide
Form separated with lithium, magnesium.It is filtered after replacement stirring 0.5h, obtains 0.59m3Crude lithium liquid and 80kg nickel cobalt manganese slag.Crude lithium turns
It is as follows that type liquid Principle components analysis the results are shown in Table 6:
The crude lithium liquid Principle components analysis result of table 6
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.02 | 0.02 | 0.44 | 23.13 | 1.05 | 16.38 | 0.001 | 0.002 |
(3) heavy nickel cobalt manganese slag and 0.3m in 80kg step (2) acidleach: are added into reaction kettle3Tap water slurry is made
Slurry pH is adjusted to 2.0 with the 25kg concentrated sulfuric acid by liquid.0.5h filtering is stirred, stirring rate 250rpm/s obtains 0.35m3Acid
Immersion liquid.
(4) 5.6kg sodium fluoride, 90 DEG C of control system temperature stirrings removing calcium and magnesium: are added in the pickle liquor obtained to step (3)
It is filtered after reaction 2h, stirring rate 300rpm/s obtains 0.32m3Liquid after removing calcium and magnesium.Calcium content in liquid after removing calcium and magnesium after measured
For 0.0003g/L, content of magnesium 0.0004g/L.
(5) extract: by liquid pH value after the removing calcium and magnesium in step (4) be adjusted to 3.0, P507/ sulfonated kerosene (volume ratio 1:
3), the organic extractant that saponification degree is 65% is extracted through 8 stage countercurrents, obtains strip liquor 0.28m after 5 grades of back extraction3, wherein each ingredient
The results are shown in Table 8.
Principle components analysis result in 8 strip liquor of table
| Element | Co | Ni | Mn | Ca | Mg | Fe | Al |
| Content/(g/L) | 13.78 | 31.47 | 6.98 | 0.001 | 0.0015 | It is not detected | 0.0002 |
(6) it synthesizes presoma: being 8:1:1 by the nickel of design, cobalt, manganese molar ratio.To in step (6) with addition of sulphur in strip liquor
Sour nickel and manganese sulfate.Sodium hydroxide and ammonium hydroxide are added into reaction kettle, control system pH to 11.5, keeping reaction temperature is 65 DEG C
4h, stirring rate 150rpm/s are stirred, ball-shape nickel hydroxide cobalt manganese is obtained.
(7) it dries: ball-shape nickel hydroxide cobalt manganese manufactured in the present embodiment is obtained into 5:3:2 type through 150 DEG C of high temperature drying 5h
Ternary precursor 60.26Kg is 97% from the overall recovery for being recovered to finished product nickel cobalt manganese.The wherein rate of recovery of cobalt are as follows:
97.2%；The rate of recovery of nickel are as follows: 95.8%；The rate of recovery of manganese are as follows: 97.0%.
Embodiment 4
The present embodiment is further optimized on the basis of embodiment 3, specifically:
S1: alkalization demagging: to 0.59m obtained in step (2)30.08m is added in crude lithium liquid332% sodium hydroxide is molten
Liquid adjusts solution ph to 12.0.1h filtering is stirred, stirring rate 200rpm/s obtains 0.56m3Refine lithium liquid.Crude lithium turns
It is as follows that type liquid Principle components analysis the results are shown in Table 7:
Table 7 refines lithium liquid Principle components analysis result
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.0004 | 0.0001 | 0.0008 | 23.88 | 0.08 | 0.0001 | 0.0004 | 0.0003 |
S2: it prepares lithium carbonate: qualified lithium liquid being warming up to 90 DEG C, is then slowly added into the sodium carbonate liquor of 220g/L
0.46m3, stirring 0.5h filtering, stirring rate 200rpm/s, filter residue is washed again, drying obtains the production of 71.29kg lithium carbonate
Product.Lithium carbonate product technical indicator is shown in Table 13,14 in the present embodiment.
Embodiment 5
(1) magnesium salts makes the transition: removing calcium and magnesium slag 200kg and 0.5m3Magnesium ion concentration is made of 82.12g/L magnesium nitrate solution
Slurries, the additional amount of magnesium salts is cobalt, nickel, manganese, lithium all leach required theoretical amount in calcium and magnesium slag 1.2 times, then dense with 15L
The pH value of system is adjusted to 4.0 by sulfuric acid.Heating is opened, keeps system temperature to filter after 85 DEG C of stirring 1h, stirring rate is
400rpm/s obtains 0.54m3Make the transition liquid.It is as follows that transition liquid Principle components analysis the results are shown in Table 9:
The transition liquid Principle components analysis result of table 9
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 11.2 | 21.03 | 9.63 | 26.6 | 0.75 | 12.03 | 0.004 | 0.003 |
(2) precipitate cobalt nickel manganese: the 0.54m of step (1) is pressed3Cobalt, nickel, manganese are wholly converted into hydroxide nickel cobalt manganese in transition liquid
1.05 times of addition potassium hydroxide 45.95kg of theoretical amount needed for calculating by chemical equation, make cobalt nickel manganese with hydroxide
The form of object is separated with lithium, magnesium.It is filtered after stirring 0.5h at 25 DEG C, stirring rate 350rpm/s obtains 0.52m3Crude lithium
Liquid and 115kg nickel cobalt manganese slag.It is as follows that crude lithium liquid Principle components analysis the results are shown in Table 10:
The crude lithium liquid Principle components analysis result of table 10
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.08 | 0.07 | 0.21 | 27.07 | 0.56 | 14.08 | 0.003 | 0.002 |
(3) heavy nickel cobalt manganese slag and 0.4m in 115kg step (2) acidleach: are added into reaction kettle3Tap water slurry is made
Slurry pH is adjusted to 1.5 with 18kg nitric acid by liquid.0.5h filtering is stirred, stirring rate 200rpm/s obtains 0.43m3Acidleach
Liquid.
(4) 7.8kg sodium fluoride, 85 DEG C of control system temperature stirrings removing calcium and magnesium: are added in the pickle liquor obtained to step (3)
It is filtered after reaction 2h, stirring rate 200rpm/s obtains 0.41m3Liquid after removing calcium and magnesium.Calcium content in liquid after removing calcium and magnesium after measured
For 0.0002g/L, content of magnesium 0.0001g/L.
(5) extract: by liquid pH value after the removing calcium and magnesium in step (4) be adjusted to 4.0, P507/ sulfonated kerosene (volume ratio 1:
3), the organic extractant that saponification degree is 70% is extracted through 8 stage countercurrents, obtains strip liquor 0.22m after 5 grades of back extraction3, wherein each ingredient
The results are shown in Table 12.
Principle components analysis result in 12 strip liquor of table
| Element | Co | Ni | Mn | Ca | Mg | Fe | Al |
| Content/(g/L) | 27.08 | 50.99 | 23.14 | 0.002 | 0.002 | It is not detected | 0.0004 |
(6) it synthesizes presoma: being 6:2:2 by the nickel of design, cobalt, manganese molar ratio.To in step (6) with addition of sulphur in strip liquor
Sour nickel and manganese sulfate.Sodium hydroxide and ammonium hydroxide are added into reaction kettle, control system pH to 11.0, keeping reaction temperature is 70 DEG C
4h, stirring rate 200rpm/s are stirred, ball-shape nickel hydroxide cobalt manganese is obtained.
(7) it dries: ball-shape nickel hydroxide cobalt manganese manufactured in the present embodiment is obtained into 6:2:2 type through 150 DEG C of high temperature drying 5h
Ternary precursor 46.51Kg is 98% from the overall recovery for being recovered to finished product nickel cobalt manganese.The wherein rate of recovery of cobalt are as follows:
98.5%；The rate of recovery of nickel are as follows: 98.8%；The rate of recovery of manganese are as follows: 97.9%.
Embodiment 6
The present embodiment is further optimized on the basis of embodiment 5, specifically:
S1: alkalization demagging: to 0.59m obtained in step (2)30.08m is added in crude lithium liquid332% sodium hydroxide is molten
Liquid adjusts solution ph to 12.5.1h filtering is stirred, stirring rate 150rpm/s obtains 0.53m3Refine lithium liquid.Refine lithium liquid
It is as follows that Principle components analysis the results are shown in Table 11:
Table 11 refines lithium liquid Principle components analysis result
| Element | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | It is not detected | It is not detected | 0.0002 | 26.56 | 0.22 | 0.0003 | 0.0001 | 0.0003 |
S2: it prepares lithium carbonate: purification lithium liquid being heated to 95 DEG C, is then slowly added into the sodium carbonate liquor of 240g/L
0.49m3, stirring 0.5h filtering, stirring rate 200rpm/s, filter residue is washed again, drying obtains the production of 73.55kg lithium carbonate
Product.Lithium carbonate product technical indicator is shown in Table 13,14 in the present embodiment.
It see the table below 13 according to the rate of recovery value of 2,4,6 pairs of nickel of embodiment, cobalt, manganese, lithium:
The rate of recovery of table 13 embodiment 2,4,6 pairs of nickel, cobalt, manganese, lithium
The chemical composition analysis of 1,3,5 lithium carbonate of the embodiment of the present invention is shown in Table 14:
14 battery-level lithium carbonate technical target of the product of table
From table 13,14 it is found that the main content of lithium carbonate made from embodiment 1,3,5 is above 99%, meet YS/T
582-2006 LITHIUM BATTERY standard requirements, wherein the main content of lithium carbonate made from embodiment 1 is up to 99.61%, and quality is high；It is real
Apply 2,4,6 pairs of nickel of example, cobalt, manganese, lithium rate of recovery value be above 95%, overall recovery is higher than 97%, wherein in embodiment 6: total
The rate of recovery is up to 98.5%, and the rate of recovery of nickel is up to 98.80%, also found through experiment test, nickel in crude lithium liquid in the present invention
The content of cobalt is 100ppm hereinafter, the content of lithium is 0.1% or less in nickel cobalt manganese slag；Traditional lithium fluoride and removing calcium and magnesium
Slag recycling lithium is not directed to the recycling of valuable metal nickel cobalt, and the present invention is by introducing heavy nickel cobalt process, to realize nickel, cobalt and lithium
Separation, the rate of recovery for reaching the comprehensive reutilization of resource and valuable metal is high.
Claims (10)
1. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material, characterized by the following steps:
(1) magnesium salts makes the transition, and slurries are made in the magnesium salt solution that removing calcium and magnesium slag and magnesium ion concentration are 30-100g/L, are added inorganic
Acid, regulation system pH are 1.0-5.0, heating stirring 1-5h, and filtering obtains transition liquid and is fluorinated calcium and magnesium slag；
(2) it sinks cobalt nickel manganese, precipitating reagent is added in the transition liquid in step (1), control system temperature is 25-100 DEG C, obtains nickel
Cobalt manganese slag and crude lithium liquid；
(3) acidleach nickel cobalt manganese slag, by step (2) nickel cobalt manganese slag and tap water size mixing, control liquid consolidate mass ratio as 2-5:1,
Slurry is made, inorganic acid is added into slurry, adjusting pH is 0-5, is stirred to react 0.5-1h, obtains pickle liquor and acid leaching residue；
(4) removing calcium and magnesium: being added soluble fluoride salt dissolving in the pickle liquor obtained to step (3), 50-100 DEG C of control system temperature is stirred
It is filtered after mixing reaction 0.5-2h, obtains deliming magnesium liquid and removing calcium and magnesium slag；
(5) it extracts: obtaining the back extraction of the manganese of nickel containing cobalt with the metallic cobalt nickel manganese in organic extractant removing calcium with solvent extraction magnesium liquid, then through back extraction
Liquid；
(6) it synthesizes presoma: into the strip liquor of step (5) with addition of cobalt nickel manganese soluble-salt, sodium hydroxide and ammonium hydroxide, control is added
System pH to 9-12 processed, keeping reaction temperature is that 60-70 DEG C of stirring 1-5h obtains ball-shape nickel hydroxide cobalt manganese；
(7) dry: ball-shape nickel hydroxide cobalt manganese described in step (6) obtains ternary forerunner through 100-500 DEG C of high temperature drying 2-5h
Body material.
2. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 1, feature
Be: cobalt in removing calcium and magnesium slag described in step (1), nickel, manganese, lithium mass percent be respectively 1-10%.
3. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 2, feature
It is: in the step (1), including at least one following technical characteristic:
It is 2-5:1 that the removing calcium and magnesium slag and the liquid of magnesium salts slurrying, which consolidate mass ratio,；
The temperature of the heating stirring is 50-100 DEG C；
The stirring rate of the heating stirring are as follows: 100-400rpm/s；
The magnesium salts is at least one of magnesium sulfate, magnesium nitrate, magnesium chloride；
The additional amount of the magnesium salts is that cobalt, nickel, manganese, lithium are wholly converted into soluble-salt by chemical reaction equation in fluorination calcium and magnesium slag
1.1-2.0 times of theoretical quality needed for formula calculates.
4. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 3, feature
Be: in step (2), the precipitating reagent is at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide；The precipitating reagent adds
Entering amount is that cobalt, nickel, manganese are wholly converted into theoretical quality needed for hydroxide is calculated by chemical equation in transition liquid
1.0-2.0 again.
5. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 4, feature
Be: the inorganic acid in step (1) and (3) is at least one of sulfuric acid, nitric acid, hydrochloric acid.
6. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 5, feature
It is: includes at least one following technical characteristic in step (4):
The soluble fluoride salt dissolving is at least one of sodium fluoride, ammonium fluoride；
Control reaction system pH is 0-5；
Stirring rate is 100-400rpm/s.
7. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 6, feature
Be: deliming magnesium liquid pH value in the step (5) is 3.0-6.0, the organic extractant is P507, sulfonated kerosene it is organic
Mixture, volume ratio 1:1-5, saponification degree 40%-70%.
8. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 7, feature
It is: by the cobalt nickel mn sulphate system that nickel cobalt manganese molar ratio is needed for 8:1:1 or 6:2:2 or 5:2:3 is incorporated in the step (6)
Standby ternary precursor material, the ternary precursor material are Ni0.8Co0.1Mn0.1(OH)2Type or Ni0.6Co0.2Mn0.2(OH)2Type
Or Ni0.5Co0.2Mn0.3(OH)2Type.
9. a kind of removing calcium and magnesium slag recycling lithium according to claim 1-4 and the side for preparing ternary precursor material
Method, it is characterised in that: further comprising the steps of:
S1: the agent of alkali formula is added in the crude lithium liquid in step (2) for alkalization demagging, adjusts solution ph to 10.0-13.0, mistake
Filter obtains purification lithium liquid and magnesium hydroxide slag；
S2: preparing lithium carbonate, and sodium carbonate liquor is added into purification lithium liquid made from step S1, lithium is made to sink in the form of lithium carbonate
Shallow lake comes out, and battery-level lithium carbonate is made after washed, drying.
10. a kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material according to claim 9, feature
Be: alkali formula agent is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide in the step S1.
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