CN107934999A - A kind of method that battery-level lithium carbonate is recycled in the catalyst waste slag from polyphenylene sulfide - Google Patents
A kind of method that battery-level lithium carbonate is recycled in the catalyst waste slag from polyphenylene sulfide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of method that battery-level lithium carbonate is recycled in catalyst waste slag from polyphenylene sulfide, this method includes eight steps altogether, first with absolute ethyl alcohol or the dissolving lithium salts of the solution containing absolute ethyl alcohol, other salt are retained in residue, reach Li and Na, Ca, Mg, the purpose of the impurity initial gross separation such as K, solid is dissolved with water again, absolute ethyl alcohol dissolution lithium salts is used again after filtrate drying, and merge with the lithium salt solution in the first step, carbonate sinker is carried out in ethanol is solvent carrier, the washed dry acquisition battery-level lithium carbonate of solid, solution drying obtains crude salt addition product.The method of the present invention, which breaks through conventional method, can not recycle complicated waste residue acquisition battery-level lithium carbonate, or need to add impurity removal reagents purifying, of high cost, complicated, and solubility product causes greatly the not high limitation of yield in water because of lithium carbonate.There is very big application value in battery material field.
Description
Technical field
The invention belongs to battery material field, and in particular to one kind recycles LITHIUM BATTERY carbon from polyphenylene sulfide catalyst waste slag
The method of sour lithium.
Background technology
Polyphenylene sulfide (PPS) is a kind of thermoplastic special engineering plastic, is given birth in production process, it is necessary to add lithium chloride and be used as
Auxiliary agent (catalyst) is produced, and lithium chloride is not consumed in process of production, finally together with other products, is discharged as waste material.
Since lithium salts is expensive, numerous studies have been done to the recovery technology of the partial oxidation lithium both at home and abroad.
In general, the method for lithium chloride is mainly to add a large amount of water to mix with waste material in prior art recycling PPS waste residues,
Water soluble salt is stayed in filtrate after separation of solid and liquid, is added impurity removal reagents to filtrate and is precipitated foreign ion and filters off, then to solution
Middle addition carbonate sinker, obtains lithium carbonate.
For example, patent application CN1345892 discloses the recovery technology of solvent and catalyst in a kind of PPS productions, the party
Method directly soaks residue with carbonate solution, and it is to recycle to obtain lithium chloride to filter after carbonate with acid acidifying, and high income is up to 90%
More than., but this method does not have removal step, and substantial amounts of magnesium, iron, calcium certainly will be remained in regenerant, and impurity content is very high
Battery-level lithium carbonate is prepared into also need to further increase subsequent technique.
The patent application of Publication No. CN101205298 is disclosed to be added in the distillation residual liquid that production PPS resin produces
A large amount of water can sedimentation separation and recycling PPS oligomer, the filtrate obtained after separation is through removal of impurities, including demagging, iron, calcium and sulfate radical
Ion, then can be such that lithium chloride is precipitated in the form of lithium carbonate, be separated with other water soluble salts, finally toward addition sodium carbonate in filtrate
Lithium compound can be recycled in the form of lithium carbonate.This method adds extra hydroxide, oxalates and barium in removal step
On the one hand the impurity removal reagents such as salt may cause portion to improve the purity of lithium carbonate since lithium oxalate solubility is not too much high
Lithium ion is divided together to be removed the reduction rate of recovery with impurity in the form of lithium oxalate, on the other hand addition and remaining calcium ion and barium
Ion can go out in next step sodium carbonate sinker with lithium carbonate coprecipitation, cause lithium carbonate purity not high, it is impossible to reach battery
The requirement of level lithium carbonate, and this is also the common drawback that such method has.
Patent application CN102675683A discloses a kind of method that NMP and catalyst are recycled by 7 steps, and catalyst returns
High income is up to more than 98%, and purity is higher than 99.9%, but the method is dependent on screw conveyor and with star-like feeder
Spiral evaporator the dope containing catalyst is handled, conventional equipment is more difficult to dope processing.And should
Method lacks removal step, is suitable only for that component is simple, such as the mainly catalyst waste slag containing sodium salt and lithium salts in this application, to containing
The waste residue for having potassium, magnesium, iron or calcium is handled, and purity will substantially reduce.
The content of the invention
For the prior art in terms of lithium salts is recycled existing deficiency, it is an object of the invention to provide one kind from polyphenylene sulfide
The method that battery-level lithium carbonate is recycled in ether catalyst waste residue.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of method that battery-level lithium carbonate is recycled in catalyst waste slag from polyphenylene sulfide, including step：
1) filter, obtain after solution of the PPS catalyst waste slags with absolute ethyl alcohol or containing absolute ethyl alcohol is sufficiently mixed
Solid and liquid；
2) solid for obtaining step 1) filters after being sufficiently mixed with water, obtains solid and liquid；
3) liquid concentration for obtaining step 2) filters, and obtains solid, then obtained solid is dried；
4) solution of the dried solid with absolute ethyl alcohol or containing absolute ethyl alcohol in step 3) is mixed, filters, obtain
To solid and liquid；
5) combining step 1) and the liquid that 4) obtains, which is lithium chloride solution；
6) add sodium carbonate into the liquid of step 5) or wet chemical is reacted, solid is obtained by filtration after reaction
And liquid：
7) solid obtained in step 6) is stirred with water and washed, obtain lithium carbonate solid and mother liquor；
8) lithium carbonate product is obtained after the lithium carbonate that step 7) obtains is dried, mother liquor is evaporated obtains solid together with step 4)
Auxiliary product NaCl or KCl are obtained after drying in the lump.
Some according to the present invention specific embodiments, recycle battery-level lithium carbonate in the above-mentioned catalyst waste slag from polyphenylene sulfide
Method, PPS catalyst waste slags contain 1-5%SO4 2-, 10-20%Na+, 0-5%K+, 0-5%Ca2+, 0-2%Mg2+, 0-2%
Fe2+。
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, PPS catalyst gives up in step 1)
The solid-to-liquid ratio that solution of the slag with absolute ethyl alcohol or containing absolute ethyl alcohol mixes is：1:10~10:1, mixing temperature is：20-100
DEG C, incorporation time 10-300min.
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, solid is mixed with water in step 2)
Solid-to-liquid ratio be：1:10~10:1, mixing temperature is：20-100 DEG C, incorporation time 10-300min.
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, solid and anhydrous second in step 4)
Alcohol or containing absolute ethyl alcohol solution mixing solid-to-liquid ratio be：1:10~10:1, mixing temperature is：20~100 DEG C, during mixing
Between be 10~300min.
In the above-mentioned catalyst waste slag from polyphenylene sulfide recycle battery-level lithium carbonate method, step 5) lithium chloride solution it is dense
Spend for 25-220g/L.
Solution of the present invention containing absolute ethyl alcohol is ethanol water.
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, step 6) add sodium carbonate or carbon
The concentration of sour aqueous solutions of potassium is 100-330g/L, and the amount of addition is-the 20% to 150% of reaction excess coefficient completely, reaction temperature
Spend for 20-100 DEG C, reaction time 10-300min.
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, step 7) are stirred with water and wash solid
When, solid-to-liquid ratio 2:1~1:20, temperature is 20-100 DEG C, stirs and washes 10~300min of time.
The method that battery-level lithium carbonate is recycled in the above-mentioned catalyst waste slag from polyphenylene sulfide, step 8) lithium carbonate drying temperature
For 80-400 DEG C, time 0.5-48h；80-400 DEG C of sodium chloride drying temperature, time 0.5-48h.
The method of the present invention, in step 1) with absolute ethyl alcohol or the dissolving PPS catalyst waste slags of the solution containing absolute ethyl alcohol
Li salt, and other salt are retained in residue, reach the separated purpose of the impurity such as Li and Na, Ca, Mg, K, avoid the prior art
It must play a significant role for battery-level lithium carbonate is made, also subtract in a variety of shortcomings that subsequent step addition impurity removal reagents are brought
It is small when being dissolved with water because lithium carbonate solubility product is larger in water causes to precipitate the low loss of the incomplete rate of recovery；Step 4) is used
The dry solid of absolute ethyl alcohol dissolving, the lithium salts that step 1) is not fully dissolved out recycle again, improve the rate of recovery, while preliminary point
From NaCl, KCl, CaCl in gained LiCl crude products2、MgCl2Deng impurity；Carrier of the step 6) by the use of ethanol as sinker solution, carbon
Solubility is low compared with water in ethanol for sour lithium, therefore solution need not be heated as traditional handicraft and can guarantee that solution
In remaining lithium it is relatively low, with reference to other steps processing so that gained lithium carbonate each impurity element index meet LITHIUM BATTERY carbon
Sour lithium standard, this can not be realized with water or other solvents.
Brief description of the drawings
Fig. 1 is the process flow chart of the method for the present invention.
Embodiment
Recycling raw material PPS catalyst waste slags according to the present invention, the catalyst waste slag being primarily referred to as in PPS production processes
Deng.Its approximate composition is as shown in table 1 below：
Table 1
| Moisture content | CO3 2- | HCO3 - | Acid non-soluble substance | Water-insoluble | Li+ | SO4 2- | Cl- | Na+ | K+ | Organic matter |
| 0.29 | 1-10 | 1-5 | 0-8 | 0-8 | 2-10 | 1-5 | 50-60 | 10-20 | 0-5 | It is some |
The method of the present invention can be handled, and by weight, contain 1-5%SO4 2-, 10-20%Na+, 0-5%K+, 0-5%
Ca2+, 0-2%Mg2+, 0-2%Fe2+Complicated component catalyst waste slag, and pass through simple and practicable operation, the carbon of recycling
Sour lithium can reach LITHIUM BATTERY standard.
The method that the present invention recycles battery-level lithium carbonate from polyphenylene sulfide catalyst waste slag, comprises the following steps, technique
Flow is referring to Fig. 1：
1) filter, obtain after solution of the PPS catalyst waste slags with absolute ethyl alcohol or containing absolute ethyl alcohol is sufficiently mixed
Solid and liquid；
2) solid for obtaining step 1) filters after being sufficiently mixed with water, obtains solid and liquid；
3) liquid concentration for obtaining step 2) filters, and obtains solid, then obtained solid is dried；
4) solution of the dried solid with absolute ethyl alcohol or containing absolute ethyl alcohol in step 3) is mixed, filters, obtain
To solid and liquid；
5) combining step 1) and the liquid that 4) obtains, which is lithium chloride solution；
6) add sodium carbonate into the liquid of step 5) or wet chemical is reacted, solid is obtained by filtration after reaction
And liquid：
7) solid obtained in step 6) is stirred with water and washes secondary, obtain lithium carbonate solid and mother liquor；
8) lithium carbonate product is obtained after the lithium carbonate that step 7) obtains is dried, mother liquor is evaporated obtains solid together with step 4)
Auxiliary product NaCl or KCl crude product is obtained after drying in the lump.
According to some embodiments of the present invention, above-mentioned steps 1), solid-to-liquid ratio 2), 4) be：1:10~10:1, mixing temperature
For：20-100 DEG C, incorporation time 10-300min.
In the above method, preferred steps 6) concentration that adds sodium carbonate liquid is 100-330g/L, the amount of addition is complete
- the 20% to 150% of excess coefficient is reacted, reaction temperature is 20-100 DEG C, reaction time 10-300min.Step 7) water
Stir when washing solid, solid-to-liquid ratio 2:1―1:20, temperature is 20-100 DEG C, stirs and washes 10-300min of time.Step 8) lithium carbonate is done
Dry temperature is 80-400 DEG C, time 0.5-48h；80-400 DEG C of sodium chloride or potassium chloride drying temperature, time 0.5-48h.
Explained below by way of specific embodiment is further to the content of the invention of the present invention, but should not be construed as the present invention
Scope be only limitted to following example, invention thinking according to the present invention and entire contents, can will be each in following instance
Technical characteristic makes appropriate combination/replacement/adjustment/modification etc., this is will be obvious to those skilled in the art that still
Belong to the category that the present invention protects.
Embodiment 1
(1) PPS catalyst waste slags and absolute ethyl alcohol are first pressed into solid-to-liquid ratio 1:1 is mixed in container, is fully stirred at 30 DEG C
Mixing is mixed, after reacting 2h, filtering, respectively obtains solid liquid phase；
(2) solid for obtaining step (1), by solid-to-liquid ratio 1:1 is mixed in container with tap water, is fully stirred at 50 DEG C
Mixing is mixed, after reacting 3h, filtering, respectively obtains solid liquid phase；
(3) liquid for obtaining step (2), by being concentrated by evaporation, cooled and filtered, obtained solid is dried；
(4) solid for obtaining step (3), by solid-to-liquid ratio 1:1 in absolute ethyl alcohol with being mixed in container, in 30 DEG C of temperature
Under be thoroughly mixed, react the 2h times after, filtering, respectively obtain solid liquid phase；
(5) liquid for obtaining step (4), the liquid obtained with step (1) mix；
(6) sodium carbonate liquor that concentration is 100g/L is added in the liquid obtained to step (5), the amount of addition is to be excessive
Number -20%, reaction temperature are 50 DEG C, reaction time 100min.It is separated by filtration to obtain the mixing of lithium carbonate and solid sodium chloride
Thing and mother liquor；
(7) hybrid solid obtained in step 6 stir washing, it is solid-to-liquid ratio 2 to stir the ratio of washing:1, stir and wash 25 DEG C of temperature,
Stir and wash time 10min.Stir wash it is secondary after the completion of, separation of solid and liquid obtains lithium carbonate wet product and stirs wash water；
(8) lithium carbonate obtained in step 7 is dried, 100 DEG C of drying temperature, drying time 2h, obtains lithium carbonate
Product；NaCl solids in step 4 are dried, 100 DEG C of drying temperature, drying time 2h, obtains NaCl auxiliary products.
By above-mentioned technique, the rate of recovery of lithium chloride is up to 85.1%, and quality reaches battery-level lithium carbonate standard, and analysis data are shown in
Table 2.
Embodiment 2
(1) PPS catalyst waste slags and absolute ethyl alcohol are first pressed into solid-to-liquid ratio 1:2 are mixed in container, are fully stirred at 40 DEG C
Mixing is mixed, after reacting 3h, filtering, respectively obtains solid liquid phase；
(2) solid for obtaining step (1), by solid-to-liquid ratio 1:2 are mixed in container with tap water, are fully stirred at 30 DEG C
Mixing is mixed, after reacting 2h, filtering, respectively obtains solid liquid phase；
(3) liquid for obtaining step (2), by being concentrated by evaporation, cooled and filtered, obtained solid is dried；
(4) solid for obtaining step (3), by solid-to-liquid ratio 1:2 in absolute ethyl alcohol with being mixed in container, in 30 DEG C of temperature
Under be thoroughly mixed, react the 2h times after, filtering, respectively obtain solid liquid phase；
(5) liquid for obtaining step (4), the liquid obtained with step (1) mix；
(6) solution of potassium carbonate that concentration is 150g/L is added in the liquid obtained to step (5), the amount of addition is to be excessive
Number 0%, reaction temperature are 60 DEG C, reaction time 120min.It is separated by filtration to obtain the mixture of lithium carbonate and solid potassium chloride
And mother liquor；
(7) hybrid solid obtained in step 6 stir washing, it is solid-to-liquid ratio 1 to stir the ratio of washing:1, stir and wash temperature 50 C,
Stir and wash time 30min.Stir wash it is secondary after the completion of, separation of solid and liquid obtains lithium carbonate wet product and stirs wash water；
(8) lithium carbonate obtained in step 7 is dried, 110 DEG C of drying temperature, drying time 2.5h, obtains carbonic acid
Lithium product；KCl solids in step 4 are dried, 110 DEG C of drying temperature, drying time 2.5h, obtains KCl auxiliary products.
By above-mentioned technique, the rate of recovery of lithium chloride is up to 84.7%, and quality reaches battery-level lithium carbonate standard, and analysis data are shown in
Table 2.
Embodiment 3
(1) PPS catalyst waste slags and absolute ethyl alcohol are first pressed into solid-to-liquid ratio 1:2 are mixed in container, are fully stirred at 40 DEG C
Mixing is mixed, after reacting 3h, filtering, respectively obtains solid liquid phase；
(2) solid for obtaining step (1), by solid-to-liquid ratio 1:3 are mixed in container with tap water, are fully stirred at 30 DEG C
Mixing is mixed, after reacting 3h, filtering, respectively obtains solid liquid phase；
(3) liquid for obtaining step (2), by being concentrated by evaporation, cooled and filtered, obtained solid is dried；
(4) solid for obtaining step (3), by solid-to-liquid ratio 1:2 in absolute ethyl alcohol with being mixed in container, in 30 DEG C of temperature
Under be thoroughly mixed, react the 2h times after, filtering, respectively obtain solid liquid phase；
(5) liquid for obtaining step (4), the liquid obtained with step (1) mix；
(6) sodium carbonate liquor that concentration is 180g/L is added in the liquid obtained to step (5), the amount of addition is to be excessive
Number -15%, reaction temperature are 55 DEG C, reaction time 110min.It is separated by filtration to obtain the mixing of lithium carbonate and solid sodium chloride
Thing and mother liquor；
(7) hybrid solid obtained in step 6 stir washing, it is solid-to-liquid ratio 1 to stir the ratio of washing:2, stir and wash 75 DEG C of temperature,
Stir and wash time 40min.Stir wash it is secondary after the completion of, separation of solid and liquid obtains lithium carbonate wet product and stirs wash water；
(8) lithium carbonate obtained in step 7 is dried, 120 DEG C of drying temperature, drying time 2h, obtains lithium carbonate
Product；NaCl solids in step 4 are dried, 120 DEG C of drying temperature, drying time 2h, obtains NaCl auxiliary products.
By above-mentioned technique, the rate of recovery of lithium chloride is up to 87.2%, and quality reaches battery-level lithium carbonate standard, and analysis data are shown in
Table 2.
Embodiment 4
(1) PPS catalyst waste slags and the liquid containing absolute ethyl alcohol are first pressed into solid-to-liquid ratio 1:4 are mixed in container, 20
It is thoroughly mixed at DEG C, after reacting 5h, filtering, respectively obtains solid liquid phase；
(2) solid for obtaining step (1), by solid-to-liquid ratio 5:1 is mixed in container with tap water, at 100 DEG C fully
It is stirred, after reacting 10min, filtering, respectively obtains solid liquid phase；
(3) liquid for obtaining step (2), by being concentrated by evaporation, cooled and filtered, obtained solid is dried；
(4) solid for obtaining step (3), by solid-to-liquid ratio 1:8 in absolute ethyl alcohol with being mixed in container, in 10 DEG C of temperature
Under be thoroughly mixed, react the 3h times after, filtering, respectively obtain solid liquid phase；
(5) liquid for obtaining step (4), the liquid obtained with step (1) mix；
(6) solution of potassium carbonate that concentration is 300g/L is added in the liquid obtained to step (5), the amount of addition is to be excessive
Number 5%, reaction temperature are 95 DEG C, reaction time 150min.It is separated by filtration to obtain the mixture of lithium carbonate and solid potassium chloride
And mother liquor；
(7) hybrid solid obtained in step 6 stir washing, it is solid-to-liquid ratio 1 to stir the ratio of washing:3, stir and wash 90 DEG C of temperature,
Stir and wash time 45min.Stir wash it is secondary after the completion of, separation of solid and liquid obtains lithium carbonate wet product and stirs wash water；
(8) lithium carbonate obtained in step 7 is dried, 110 DEG C of drying temperature, drying time 4h, obtains lithium carbonate
Product；NaCl solids in step 4 are dried, 110 DEG C of drying temperature, drying time 4h, obtains KCl auxiliary products.
By above-mentioned technique, the rate of recovery of lithium chloride is up to 90.3%, and quality reaches battery-level lithium carbonate standard, and analysis data are shown in
Table 2.
Embodiment 5
(1) PPS catalyst waste slags and the liquid containing absolute ethyl alcohol are first pressed into solid-to-liquid ratio 1:10 are mixed in container,
It is thoroughly mixed at 100 DEG C, after reacting 1h, filtering, respectively obtains solid liquid phase；
(2) solid for obtaining step (1), by solid-to-liquid ratio 10:1 is mixed in container with tap water, at 20 DEG C fully
It is stirred, after reacting 5h, filtering, respectively obtains solid liquid phase；
(3) liquid for obtaining step (2), by being concentrated by evaporation, cooled and filtered, obtained solid is dried；
(4) solid for obtaining step (3), by solid-to-liquid ratio 1:6 in absolute ethyl alcohol with being mixed in container, in 30 DEG C of temperature
Under be thoroughly mixed, react the 2h times after, filtering, respectively obtain solid liquid phase；
(5) liquid for obtaining step (4), the liquid obtained with step (1) mix；
(6) sodium carbonate liquor that concentration is 330g/L is added in the liquid obtained to step (5), the amount of addition is to be excessive
Number 50%, reaction temperature are 98 DEG C, reaction time 150min.It is separated by filtration to obtain sodium carbonate and the mixture of solid sodium chloride
And mother liquor；
(7) hybrid solid obtained in step 6 stir washing, it is solid-to-liquid ratio 1 to stir the ratio of washing:20, stir and wash 98 DEG C of temperature,
Stir and wash time 60min.Stir wash it is secondary after the completion of, separation of solid and liquid obtains lithium carbonate wet product and stirs wash water；
(8) lithium carbonate obtained in step 7 is dried, 110 DEG C of drying temperature, drying time 4.5h, obtains carbonic acid
Lithium product；NaCl solids in step 4 are dried, 110 DEG C of drying temperature, drying time 4.5h, obtains NaCl auxiliary products.
By above-mentioned technique, the rate of recovery of lithium chloride is up to 91.7%, and quality reaches battery-level lithium carbonate standard, and analysis data are shown in
Table 2.
Table 2
Claims (10)
1. the method for battery-level lithium carbonate is recycled in a kind of catalyst waste slag from polyphenylene sulfide, it is characterised in that including following step
Suddenly：
1) filtered after solution of the PPS catalyst waste slags with absolute ethyl alcohol or containing absolute ethyl alcohol is sufficiently mixed, obtain solid
And liquid；
2) solid for obtaining step 1) filters after being sufficiently mixed with water, obtains solid and liquid；
3) liquid concentration for obtaining step 2) filters, and obtains solid, then obtained solid is dried；
4) solution of the dried solid with absolute ethyl alcohol or containing absolute ethyl alcohol in step 3) is mixed, filtered, consolidate
Body and liquid；
5) combining step 1) and the liquid that 4) obtains, which is lithium chloride solution；
6) add sodium carbonate into the liquid of step 5) or wet chemical is reacted, solid and liquid are obtained by filtration after reaction
Body：
7) solid obtained in step 6) is stirred with water and washed, obtain lithium carbonate solid and mother liquor；
8) lithium carbonate product is obtained after the lithium carbonate that step 7) obtains is dried, mother liquor is evaporated obtains solid in the lump together with step 4)
Auxiliary product NaCl or KCl are obtained after drying.
2. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the PPS catalyst waste slags contain 1-5%SO4 2-, 10-20%Na+, 0-5%K+, 0-5%Ca2+, 0-2%Mg2+、0-
2%Fe2+。
3. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the solid-to-liquid ratio that solution of the PPS catalyst waste slags with absolute ethyl alcohol or containing absolute ethyl alcohol mixes in step 1) is：1:10
~10:1, mixing temperature is：20-100 DEG C, incorporation time 10-300min.
4. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the solid-to-liquid ratio that solid is mixed with water in step 2) is：1:10~10:1, mixing temperature is：20-100 DEG C, incorporation time is
10-300min。
5. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the solid-to-liquid ratio that solution of the solid with absolute ethyl alcohol or containing absolute ethyl alcohol mixes in step 4) is：1:10~10:1, mix
Closing temperature is：20~100 DEG C, incorporation time is 10~300min.
6. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the concentration of step 5) lithium chloride solution is 25-220g/L.
7. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, the solution containing absolute ethyl alcohol is ethanol water.
8. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, it is 100-330g/L that step 6), which adds sodium carbonate or the concentration of potassium carbonate liquid, and the amount of addition is the excessive system of reaction completely
Several -20% is to 150%, and reaction temperature is 20-100 DEG C, reaction time 10-300min.
9. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, step 7) is stirred with water when washing solid, solid-to-liquid ratio 2:1~1:20, temperature be 20~100 DEG C, stir wash the time 10~
300min。
10. the method for battery-level lithium carbonate, its feature are recycled in the catalyst waste slag according to claim 1 from polyphenylene sulfide
It is, step 8) lithium carbonate drying temperature is 80~400 DEG C, 0.5~48h of time；Sodium chloride or potassium chloride drying temperature 80~
400 DEG C, 0.5~48h of time.
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| CN109592699A (en) * | 2018-12-19 | 2019-04-09 | 中化河北有限公司 | The preparation method of LITHIUM BATTERY lithium hydroxide |
| CN114566729A (en) * | 2022-03-04 | 2022-05-31 | 湖北亿纬动力有限公司 | Comprehensive recovery method of waste lithium iron phosphate battery |
| CN115432723A (en) * | 2022-09-05 | 2022-12-06 | 南京工程学院 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
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| CN109592699A (en) * | 2018-12-19 | 2019-04-09 | 中化河北有限公司 | The preparation method of LITHIUM BATTERY lithium hydroxide |
| CN109592699B (en) * | 2018-12-19 | 2021-10-08 | 中化国际新材料(河北)有限公司 | Preparation method of battery-grade lithium hydroxide |
| CN114566729A (en) * | 2022-03-04 | 2022-05-31 | 湖北亿纬动力有限公司 | Comprehensive recovery method of waste lithium iron phosphate battery |
| CN114566729B (en) * | 2022-03-04 | 2024-01-02 | 湖北亿纬动力有限公司 | Comprehensive recovery method of waste lithium iron phosphate battery |
| CN115432723A (en) * | 2022-09-05 | 2022-12-06 | 南京工程学院 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
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