CN115432723A - Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials - Google Patents
Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials Download PDFInfo
- Publication number
- CN115432723A CN115432723A CN202211079640.7A CN202211079640A CN115432723A CN 115432723 A CN115432723 A CN 115432723A CN 202211079640 A CN202211079640 A CN 202211079640A CN 115432723 A CN115432723 A CN 115432723A
- Authority
- CN
- China
- Prior art keywords
- lithium
- reaction
- butyllithium
- sec
- waste residues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing battery-grade lithium carbonate by taking waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials, and relates to the technical field of preparation of battery-grade lithium carbonate. Most of waste residues obtained in the lithium sand preparation stage are solid, and waste residues obtained in the lithium sand filtering and washing stage and the final synthesis reaction stage are liquid, so that the lithium is convenient to recycle.
Description
Technical Field
The invention relates to a method for preparing battery-grade lithium carbonate by taking waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials, and belongs to the technical field of preparation of battery-grade lithium carbonate.
Background
Lithium carbonate is one of the most important species of lithium compounds, from which various lithium compound products can be produced, for example: battery grade lithium carbonate. The battery-grade lithium carbonate is an important material which is necessary for preparing lithium ion batteries such as lithium iron phosphate, ternary cathode materials and the like. With the continuous temperature rise of low-carbon economy and new energy industry, especially the high-speed development of lithium ion battery industry, the demand of lithium carbonate is increasing day by day, and the price is soaring all the way.
N-butyllithium and sec-butyllithium in industrial production have good reactivity, and are mainly used as excellent initiators and catalysts for polymer industry such as synthetic rubber. The literature for large-scale production of n-butyllithium and sec-butyllithium is less, and the production method is generally that metal lithium is melted and stirred in white oil at 180-230 ℃, then rapidly cooled to form lithium sand particles, and finally filtered and washed, and then put into a synthesis reaction kettle, such as the literature US20070152354; raney, xiaoxian, sec-butyllithium synthesis [ J ], lanhua technology, 1990, 03.
In the preparation process, a certain amount of lithium-containing waste residues are generated difficultly, and in the common treatment process, the waste residues are naturally oxidized and weathered by adopting a burying mode and the like, so that certain pollution is caused to the environment, safety accidents can be caused if the environment is not noticed, and a certain amount of lithium element is wasted. Under the background of the rising price of lithium compounds, the benefit of production enterprises can be increased if the lithium element in the waste residues can be effectively utilized.
Disclosure of Invention
Aiming at the technical problem that lithium elements are not extracted by taking waste residues in the production of n-butyllithium and sec-butyllithium as raw materials, the invention designs a method for preparing battery-grade lithium carbonate by taking the waste residues in the production of the n-butyllithium and the sec-butyllithium as the raw materials to effectively treat the waste residues in the production of the n-butyllithium and the sec-butyllithium so as to realize the recovery of the lithium elements and reduce the environmental pollution.
In order to realize the purpose, the technical scheme of the invention is as follows:
a method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials comprises the following steps:
s10, collecting lithium-containing waste residues generated in each stage in the process of preparing n-butyllithium and sec-butyllithium, sending solid lithium-containing waste residues into a first reaction kettle, and obtaining a waste residue solution under the condition of excessive sulfuric acid with the mass fraction of 93-98%;
s20, under the protection of inert gas, sending the liquid lithium-containing waste residue in the lithium-containing waste residue into the first reaction kettle, keeping excessive concentrated sulfuric acid, and after full reaction, purifying the obtained solution;
s30, under the protection of inert gas, sending the solution obtained in the step S20 into a second reaction kettle, introducing carbon dioxide into the second reaction kettle, replacing the inert gas and keeping the interior of the second reaction kettle at positive pressure all the time until the carbonization reaction is finished;
the reaction conditions at least satisfy: the pH value range during the reaction is 7.5-8.5, the end point pH value is 8, the reaction time is 1-4h, the reaction temperature is 15-25 ℃, and the carbon dioxide introducing speed per 100g of lithium-containing waste residue ranges from 5-8L/h;
s40, filtering the solution obtained in the S30 to obtain a filter cake, and performing vacuum drying on the obtained filter cake to obtain battery-grade lithium carbonate;
and S50, recovering and treating the filtrate obtained after filtration in the S40 for recycling.
Preferably, the lithium-containing waste residue in S10 is obtained at least in the following equipment:
a reaction kettle for preparing lithium sand, a washing kettle for filtering and washing the lithium sand and a synthesis reaction kettle.
Preferably, the resulting solution is purified in S20 as follows:
reacting saturated carbonate solution with the obtained solution, adding excessive water to wash the collected precipitate, and collecting the solution after passing through an ion exchange membrane;
the purification process at least meets the following conditions:
the reaction temperature of the saturated carbonate solution and the obtained solution is 25-28 ℃;
when washing, the temperature of water is 60-80 ℃, and the obtained precipitate is continuously stirred when washing, wherein the stirring speed is 45-60r/min;
when passing through the ion exchange membrane, the osmotic pressure is 0.2-0.3MPa.
Preferably, the ion exchange membrane employs any one of the following:
styrene type cation exchange membranes, acrylic acid type cation exchange membranes, and vinylpyridine type cation exchange membranes.
Preferably, in S30, the internal pressure of the second reaction kettle ranges from 6.5 to 8.5X 10 after carbon dioxide is stably introduced 5 Pa, the pH value range is 7.9-8 during the reaction, the reaction time is 2-3h, the reaction temperature is 18-23 ℃, and the carbon dioxide introducing speed range of 6-7L/h per 100g of lithium-containing waste residue is realized.
Preferably, before the carbon dioxide is introduced, the introduction of the carbon dioxide is started after the temperature of the solution is cooled to 18-23 ℃;
stirring the solution at a rotation speed of 60-80r/min for 1-1.5h in the process of introducing carbon dioxide, wherein the internal pressure of the second reaction kettle reaches 6.5-8.5 multiplied by 10 5 Pa rangeAt this time, stirring was started.
Preferably, in S40, the resulting solution is filtered through a microfiltration membrane;
the microporous filter membrane adopts any one of the following components:
polyethersulfone membranes, cellulose acetate membranes, and mixed cellulose membranes.
Preferably, in S40, the filter cake is washed with water before vacuum drying;
the mass ratio of the filter cake to the washing water is 1:5.
preferably, the vacuum drying at least satisfies the following conditions:
drying at 120-180 deg.C for 2-3h until the absolute vacuum degree reaches 80.5-95.3KPa;
wherein, the time for heating from normal temperature to 70 ℃ is 0.5h;
heating from 70 deg.C to drying temperature of 120-180 deg.C for 1h;
maintaining for at least 0.5h after reaching the drying temperature, and then cooling to the normal temperature;
and (4) introducing inert protective gas in advance in the drying process to completely replace the air in the drying equipment, and stopping introducing the inert protective gas until the temperature in the drying equipment is reduced to the normal temperature.
Preferably, in S40, the following operations may also be performed on the solution obtained in S30:
carrying out pyrolysis reaction on the solution obtained in the S30 to obtain lithium carbonate crystals, and drying the lithium carbonate crystals to obtain battery-grade lithium carbonate;
the pyrolysis reaction at least meets the following conditions:
the heating temperature is 75-90 deg.C, and the heating time is 25-30min.
The invention achieves the following beneficial effects:
1. in the invention, most of the waste residues obtained in the lithium sand preparation stage are solid, and the waste residues obtained in the lithium sand filtering and washing stage and the final synthesis reaction stage are liquid, so that the lithium can be recycled conveniently;
2. in the invention, because incompletely reacted lithium ions exist in the liquid lithium-containing waste residue, inert protective gas is adopted to isolate the lithium ions from air in the processes of collection, carbonization reaction and final drying, so that other impurities are prevented from being brought in the reaction process, and the purity of the final product is greatly improved;
3. in the invention, the obtained filtrate left after filtration can be recycled and reused for recycling treatment of the lithium-containing waste residue, so that the recovery rate and the reutilization rate of the materials are improved, and the product quality is not affected due to the extremely low impurity content in the lithium-containing waste residue, so that the overall recovery cost is further reduced.
Drawings
FIG. 1 is a flow chart of a method for preparing battery-grade lithium carbonate by using waste residues in n-butyllithium and sec-butyllithium production as raw materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the present invention can be obtained commercially or from production processes.
The first embodiment is as follows:
with reference to the attached drawing 1, a method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials comprises the following steps:
step S10, collecting lithium-containing waste residues from a reaction kettle for preparing lithium sand, a washing kettle for filtering and washing the lithium sand and a synthesis reaction kettle, sending the solid lithium-containing waste residues into a first reaction kettle, and obtaining a waste residue solution under the condition of excessive sulfuric acid with the mass fraction of 95%;
step S20, under the protection of inert gas, sending liquid lithium-containing waste residues in the lithium-containing waste residues into the first reaction kettle, keeping excessive concentrated sulfuric acid, and after full reaction, purifying the obtained solution;
the resulting solution was purified as follows:
reacting saturated carbonate solution with the obtained solution, adding excessive water to wash the collected precipitate, and collecting the solution after passing through an ion exchange membrane;
the purification process at least meets the following conditions:
the reaction temperature of the saturated carbonate solution with the obtained solution was 26 ℃;
when washing, the temperature of water is 70 ℃, and when washing, the obtained precipitate is continuously stirred at the stirring speed of 52r/min;
when the ion exchange membrane is passed through, the osmotic pressure is 0.25MPa;
the ion exchange membrane adopts a styrene type cation exchange membrane;
step S30, under the protection of inert gas, sending the solution obtained in the step S20 into a second reaction kettle, introducing carbon dioxide into the second reaction kettle, replacing the inert gas and keeping the interior of the second reaction kettle at positive pressure all the time until the carbonization reaction is finished;
the internal pressure of the second reaction kettle is 7 multiplied by 10 after the carbon dioxide is stably introduced 5 Pa, the pH value during the reaction is 8, the end-point pH value is 8, the reaction time is 2.5h, the reaction temperature is 20 ℃, and the carbon dioxide introduction rate per 100g of lithium-containing waste residue is 6.5L/h;
before introducing carbon dioxide, cooling the solution to 20 ℃, and then introducing the carbon dioxide;
stirring the solution at a rotation speed of 70r/min for 1.3h in the process of introducing carbon dioxide, wherein the internal pressure of the second reaction kettle reaches 7 multiplied by 10 5 When Pa, starting stirring;
step S40, filtering the solution obtained in the step S30 through a microporous filter membrane to obtain a filter cake, and performing vacuum drying on the obtained filter cake to obtain battery-grade lithium carbonate;
the microporous filter membrane adopts a polyether sulfone membrane;
washing the obtained filter cake with water before vacuum drying;
the mass ratio of the filter cake to the washing water is 1:5;
the vacuum drying satisfies the following conditions:
drying at 150 deg.C for 2.5h until the absolute vacuum degree reaches 88.5KPa;
wherein, the time for raising the temperature from normal temperature to 70 ℃ is 0.5h;
heating from 70 deg.C to drying temperature of 150 deg.C for 1 hr;
maintaining for 1h after reaching the drying temperature, and then cooling to normal temperature;
introducing inert protective gas in advance to completely replace the air in the drying equipment in the drying process, and stopping introducing the inert protective gas until the temperature in the drying equipment is reduced to the normal temperature;
and step S50, recovering and treating the filtrate obtained after filtration in the step S40 for recycling.
At the present stage, in the recycling treatment process of the lithium slag, the lithium slag is usually required to be subjected to subsequent treatment after slurrying, however, the viscosity of the lithium slag material is large, the dispersing effect is poor in the slurrying process, reasonable dissociation of different mineral substances in the lithium slag can not be realized in the stirring process, and sufficient mixing can not be realized, so that the recycling effect is not ideal.
In the application, the lithium-containing waste residue mainly comes from a lithium sand preparation stage, a lithium sand filtering and washing stage and a final synthesis reaction stage in the production process of n-butyl lithium and sec-butyl lithium. Because the raw materials used in the preparation of the n-butyl lithium and the sec-butyl lithium are lithium, the products obtained in each stage are lithium-containing compounds, and compared with lithium ore and other lithium-containing waste residues, the lithium-containing compounds have extremely high purity, almost no common impurities such as calcium, magnesium and the like, the extraction process is relatively simple, and the impurity removal process is also reduced.
In the embodiment, solid lithium-containing waste residues are converted into liquid, hydroxyl groups of the solid lithium-containing waste residues are replaced and converted into salt solutions, and the salt solutions and the liquid waste residues are combined and subjected to carbonization reaction, and then filtered and dried to obtain the battery-grade lithium carbonate with high purity.
Because incompletely reacted lithium ions exist in the liquid lithium-containing waste residue, inert protective gas is adopted to isolate the lithium ions from air in the processes of collection, carbonization reaction and final drying, so that other impurities are prevented from being brought in the reaction process, and the purity of the final product is greatly improved.
In addition, in this technical scheme, the gained filtrating that leaves after filtering can be retrieved and recycled, is used for containing the recovery processing of lithium waste residue once more, improves the rate of recovery and the reuse rate of material, and because impurity content is few in the content waste residue, can not cause the influence to the quality of product, holistic recovery cost further reduces.
Examples two to eleven:
the procedure according to the first embodiment is different from the procedure for purifying the solution obtained, as shown in table 1:
as can be seen from table 1, the purification conditions for the resulting solution were: the reaction temperature is 26 ℃; the temperature of the water is 70 ℃; the stirring speed is 52r/min; the osmotic pressure value is 0.25MPa; when the ion exchange membrane adopts a styrene type cation exchange membrane, the recovery rate and the purity of the battery-grade lithium carbonate are optimal.
Examples twelve-twenty-one:
according to the method of carrying out one, the reaction conditions were different when carbon dioxide was introduced, as shown in Table 2:
as can be seen from table 2, the reaction conditions when carbon dioxide was introduced were: the internal pressure of the second reaction kettle is 7 multiplied by 10 5 Pa, the pH value during the reaction is 8, the end-point pH value is 8, the reaction time is 2.5h, the reaction temperature is 20 ℃, and the recovery rate and the purity of the battery-grade lithium carbonate are optimal when the carbon dioxide is introduced into every 100g of lithium-containing waste residues at a rate of 6.5L/h.
Examples twenty-two to twenty-six:
according to the method of the first embodiment, except for the difference in the operations before and during the carbon dioxide introduction, as shown in Table 3:
| examples | Temperature of the solution | Stirring at a rotating speed | Time of stirring | Complete reaction time of carbonization | Recovery rate |
| Example one | 20℃ | 70r/min | 1.3h | 2.5h | 98.32％ |
| Example twenty two | 18℃ | 70r/min | 1.3h | 2h | 97.56％ |
| Example twenty three | 23℃ | 70r/min | 1.3h | 3h | 96.84％ |
| Example twenty-four | 20℃ | 60r/min | 1.3h | 2.5h | 97.81％ |
| Example twenty-five | 20℃ | 80r/min | 1.3h | 2.5h | 97.88％ |
| Example twenty-five | 20℃ | 70r/min | 1h | 4h | 96.56％ |
| Example twenty-six | 20℃ | 70r/min | 1.5h | 2h | 97.86％ |
As can be seen from Table 3, the solution was cooled to 20 ℃ before the introduction of carbon dioxide; and in the process of introducing carbon dioxide, stirring the solution at the rotating speed of 70r/min, wherein the complete carbonization reaction time and the recovery rate are optimal when the stirring time is 1.3 h.
Examples twenty-seven to thirty-three:
according to the method of the first embodiment, there is a difference in the treatment of only the solution obtained in step S30, as shown in table 4:
as can be seen from Table 4, the microfiltration membrane is a polyethersulfone membrane; the mass ratio of the filter cake to the washing water is 1:5; the vacuum drying satisfies the following conditions: drying at 150 deg.C for 2.5h until the absolute vacuum degree reaches 88.5KPa; when the solution is maintained for 1 hour after reaching the drying temperature, the treatment effect on the solution obtained in step S30 is optimal.
Example thirty-four:
according to the method of example one, except that there is a difference in the treatment of the solution obtained in step S30 in step S40.
In this embodiment, the following operations may also be performed on the solution obtained in S30:
carrying out pyrolysis reaction on the solution obtained in the S30 to obtain lithium carbonate crystals, and drying the lithium carbonate crystals to obtain battery-grade lithium carbonate;
the pyrolysis reaction at least meets the following conditions:
the heating temperature is 82 deg.C, and the heating time is 28min.
Examples thirty-five to thirty-eight:
the procedure of example thirty-four was followed except that the pyrolysis reaction was carried out at different temperatures and for different heating times as shown in Table 5:
| examples | Temperature of heating | Time of heating | Recovery rate | Purity of |
| Example thirty-four | 82℃ | 28min | 98.31％ | 99.89％ |
| Example thirty-five | 75℃ | 28min | 97.24％ | 98.50％ |
| Example thirty-six | 90℃ | 28min | 97.91％ | 98.68％ |
| Example thirty-seven | 82℃ | 25min | 97.85％ | 99.68％ |
| Example thirty-eight | 82℃ | 30min | 97.89％ | 99.65％ |
As can be seen from table 5, the recovery rate and purity of the battery grade lithium carbonate were optimized when the temperature of the pyrolysis reaction was 82 ℃ and the heating time was 28min.
Comparative examples one to two:
the lithium carbonate content in the crude lithium carbonate product was the first comparative example, and the lithium carbonate content in the technical grade lithium carbonate product was the second comparative example, as shown in table 6.
| Purity of | |
| Example one | 99.91％ |
| Example thirty-four | 99.89％ |
| Comparative example 1 | 94.21％ |
| Comparative example No. two | 98.58％ |
As can be seen from table 6, the purity of the battery grade lithium carbonate prepared by the methods of example one and example thirty-four is higher than the lithium carbonate content in the crude lithium carbonate product and the lithium carbonate content in the industrial grade lithium carbonate product. And the purity of the battery-grade lithium carbonate prepared by the method of the first embodiment is highest.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials is characterized by comprising the following steps:
s10, collecting lithium-containing waste residues generated in each stage in the process of preparing n-butyllithium and sec-butyllithium, sending the solid lithium-containing waste residues into a first reaction kettle, and obtaining a waste residue solution under the condition of excessive sulfuric acid with the mass fraction of 93-98%;
s20, under the protection of inert gas, sending the liquid lithium-containing waste residue in the lithium-containing waste residue into the first reaction kettle, keeping excessive concentrated sulfuric acid, and after full reaction, purifying the obtained solution;
s30, under the protection of inert gas, sending the solution obtained in the step S20 into a second reaction kettle, introducing carbon dioxide into the second reaction kettle, replacing the inert gas and keeping the interior of the second reaction kettle at positive pressure all the time until the carbonization reaction is finished;
the reaction conditions at least satisfy: the pH value range during the reaction is 7.5-8.5, the end point pH value is 8, the reaction time is 1-4h, the reaction temperature is 15-25 ℃, and the carbon dioxide introduction rate per 100g of lithium-containing waste residue is 5-8L/h;
s40, filtering the solution obtained in the S30 to obtain a filter cake, and performing vacuum drying on the obtained filter cake to obtain battery-grade lithium carbonate;
and S50, recovering and treating the filtrate obtained after filtration in the S40 for recycling.
2. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1, which is characterized by comprising the following steps of:
the lithium-containing waste residue in the S10 is at least obtained in the following equipment:
a reaction kettle for preparing lithium sand, a washing kettle for filtering and washing the lithium sand and a synthesis reaction kettle.
3. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1, which is characterized by comprising the following steps of:
the purification method of the obtained solution in S20 is as follows:
reacting saturated carbonate solution with the obtained solution, adding excessive water to wash the collected precipitate, and collecting the solution after passing through an ion exchange membrane;
the purification process at least meets the following conditions:
the reaction temperature of the saturated carbonate solution and the obtained solution is 25-28 ℃;
when washing, the temperature of water is 60-80 ℃, and the obtained precipitate is continuously stirred when washing, wherein the stirring speed is 45-60r/min;
when passing through the ion exchange membrane, the osmotic pressure value range is 0.2-0.3MPa.
4. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials according to claim 3, which is characterized by comprising the following steps:
the ion exchange membrane adopts any one of the following substances:
styrene type cation exchange membranes, acrylic acid type cation exchange membranes, and vinylpyridine type cation exchange membranes.
5. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1, which is characterized by comprising the following steps of:
in S30, after the carbon dioxide is stably introduced, the internal pressure of the second reaction kettle ranges from 6.5 to 8.5 multiplied by 10 5 Pa, the pH value range is 7.9-8 during reaction, the reaction time is 2-3h, the reaction temperature is 18-23 ℃, and the carbon dioxide introduction rate range is 6-7L/h per 100g of lithium-containing waste residue.
6. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1 or 5, which is characterized by comprising the following steps of:
before introducing carbon dioxide, cooling the solution to 18-23 ℃, and then introducing the carbon dioxide;
stirring the solution at a rotation speed of 60-80r/min for 1-1.5h in the process of introducing carbon dioxide, wherein the internal pressure of the second reaction kettle reaches 6.5-8.5 multiplied by 10 5 In the Pa range, stirring was started.
7. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1, which is characterized by comprising the following steps of:
s40, filtering the obtained solution through a microporous filter membrane;
the microporous filter membrane adopts any one of the following components:
polyethersulfone membranes, cellulose acetate membranes, and mixed cellulose membranes.
8. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1, which is characterized by comprising the following steps of:
s40, washing the filter cake with water before vacuum drying;
the mass ratio of the filter cake to the washing water is 1:5.
9. the method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyl lithium and sec-butyl lithium as raw materials according to claim 1 or 8, which is characterized in that:
the vacuum drying at least meets the following conditions:
drying at 120-180 deg.C for 2-3h until the absolute vacuum degree reaches 80.5-95.3KPa;
wherein, the time for raising the temperature from normal temperature to 70 ℃ is 0.5h;
heating from 70 deg.C to drying temperature of 120-180 deg.C for 1h;
maintaining for at least 0.5h after reaching the drying temperature, and then cooling to the normal temperature;
and (4) introducing inert protective gas in advance in the drying process to completely replace the air in the drying equipment, and stopping introducing the inert protective gas until the temperature in the drying equipment is reduced to the normal temperature.
10. The method for preparing battery-grade lithium carbonate by using waste residues generated in the production of n-butyllithium and sec-butyllithium as raw materials according to claim 1, which is characterized by comprising the following steps:
in S40, the following operations may be performed on the solution obtained in S30:
carrying out pyrolysis reaction on the solution obtained in the S30 to obtain lithium carbonate crystals, and drying the lithium carbonate crystals to obtain battery-grade lithium carbonate;
the pyrolysis reaction at least meets the following conditions:
the heating temperature is 75-90 deg.C, and the heating time is 25-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211079640.7A CN115432723A (en) | 2022-09-05 | 2022-09-05 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211079640.7A CN115432723A (en) | 2022-09-05 | 2022-09-05 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115432723A true CN115432723A (en) | 2022-12-06 |
Family
ID=84246536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211079640.7A Pending CN115432723A (en) | 2022-09-05 | 2022-09-05 | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115432723A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211546A (en) * | 1998-08-26 | 1999-03-24 | 巴陵石化岳阳石油化工总厂 | Treatment method for lithium-containing waste liquid of synthetic alkyl lithium compound |
| JP2005026089A (en) * | 2003-07-02 | 2005-01-27 | Toyota Motor Corp | Lithium battery as well as manufacturing method and processing method of the same |
| CN102041380A (en) * | 2010-11-17 | 2011-05-04 | 山东瑞福锂业有限公司 | Production process for extracting lithium from ore with low-temperature method |
| CN107934999A (en) * | 2017-12-06 | 2018-04-20 | 天齐锂业股份有限公司 | A kind of method that battery-level lithium carbonate is recycled in the catalyst waste slag from polyphenylene sulfide |
| US20190144295A1 (en) * | 2017-11-14 | 2019-05-16 | Kangwon National University University-Industry Cooperation Foundation | Method of producing high-purity lithium carbonate by controlling particle size, particle size distribution, and particle shape |
| CN112678851A (en) * | 2020-12-28 | 2021-04-20 | 河南科技大学 | Preparation method of low-cost battery-grade lithium carbonate |
| CN113735143A (en) * | 2021-09-27 | 2021-12-03 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium carbonate by directly carbonizing lithium hydroxide |
| CN113912088A (en) * | 2021-09-28 | 2022-01-11 | 江西赣锋锂业股份有限公司 | Method for preparing battery-grade lithium carbonate by recovering lithium from lithium waste tert-amyl alcohol |
| CN114477245A (en) * | 2022-02-24 | 2022-05-13 | 宁夏天霖新材料科技有限公司 | Method for preparing lithium carbonate of battery by continuously carbonizing industrial-grade lithium carbonate |
| CN114702048A (en) * | 2022-03-25 | 2022-07-05 | 珠海广隆新材料科技有限公司 | Lithium slag solid waste recycling process |
-
2022
- 2022-09-05 CN CN202211079640.7A patent/CN115432723A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211546A (en) * | 1998-08-26 | 1999-03-24 | 巴陵石化岳阳石油化工总厂 | Treatment method for lithium-containing waste liquid of synthetic alkyl lithium compound |
| JP2005026089A (en) * | 2003-07-02 | 2005-01-27 | Toyota Motor Corp | Lithium battery as well as manufacturing method and processing method of the same |
| CN102041380A (en) * | 2010-11-17 | 2011-05-04 | 山东瑞福锂业有限公司 | Production process for extracting lithium from ore with low-temperature method |
| US20190144295A1 (en) * | 2017-11-14 | 2019-05-16 | Kangwon National University University-Industry Cooperation Foundation | Method of producing high-purity lithium carbonate by controlling particle size, particle size distribution, and particle shape |
| CN107934999A (en) * | 2017-12-06 | 2018-04-20 | 天齐锂业股份有限公司 | A kind of method that battery-level lithium carbonate is recycled in the catalyst waste slag from polyphenylene sulfide |
| CN112678851A (en) * | 2020-12-28 | 2021-04-20 | 河南科技大学 | Preparation method of low-cost battery-grade lithium carbonate |
| CN113735143A (en) * | 2021-09-27 | 2021-12-03 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium carbonate by directly carbonizing lithium hydroxide |
| CN113912088A (en) * | 2021-09-28 | 2022-01-11 | 江西赣锋锂业股份有限公司 | Method for preparing battery-grade lithium carbonate by recovering lithium from lithium waste tert-amyl alcohol |
| CN114477245A (en) * | 2022-02-24 | 2022-05-13 | 宁夏天霖新材料科技有限公司 | Method for preparing lithium carbonate of battery by continuously carbonizing industrial-grade lithium carbonate |
| CN114702048A (en) * | 2022-03-25 | 2022-07-05 | 珠海广隆新材料科技有限公司 | Lithium slag solid waste recycling process |
Non-Patent Citations (3)
| Title |
|---|
| 张晓峰等: "利用废锂渣制备碳酸锂", 《化工环保》, pages 25 - 28 * |
| 胡敏等: "含锂工业废料制备电池级碳酸锂工艺研究", 《无机盐工业》, pages 80 - 84 * |
| 陈武杰等: "含锂废渣制备碳酸锂", 《有色金属（冶炼部分）》, pages 71 - 74 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112342389A (en) | Method for recovering valuable metal from waste chemical catalyst | |
| CN114477245A (en) | Method for preparing lithium carbonate of battery by continuously carbonizing industrial-grade lithium carbonate | |
| CN101182079A (en) | Citric acid mother liquor treatment process | |
| CN114195315A (en) | Method for combined treatment of acidic and non-acidic copper-containing etching waste liquid, tin stripping waste liquid and copper nitrate waste liquid | |
| CN113603120A (en) | Method for recovering battery-grade lithium from waste lithium iron phosphate through short-process acid leaching | |
| CN110512075B (en) | Method for deeply purifying and removing cadmium from cobalt-manganese sulfate mixed liquid | |
| CN115432723A (en) | Method for preparing battery-grade lithium carbonate by taking waste residues generated in production of n-butyllithium and sec-butyllithium as raw materials | |
| CN114195175A (en) | Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder | |
| CN112850751A (en) | Method for recovering sodium sulfate in nicotine purification process | |
| CN111170894A (en) | Method for circularly producing urea phosphate by using wet-process phosphoric acid and urea phosphate mother liquor | |
| CN112678849A (en) | Method for preparing high-purity lithium carbonate by using lithium hydroxide | |
| CN219897130U (en) | Wet phosphoric acid double-extraction purifying device | |
| CN115215310B (en) | Impurity removal and recovery method for crude phosphoric acid | |
| CN111018008B (en) | Method for preparing battery-grade nickel hydroxide without extraction | |
| CN114702413B (en) | Process for producing sodium hydroxymethanesulfonate by using byproduct formaldehyde and sodium sulfate | |
| CN219897131U (en) | Wet phosphoric acid purifying system | |
| CN219342236U (en) | Comprehensive treatment system for copper-arsenic-rich solid waste | |
| CN114957161B (en) | Multistage washing separation method of rubber vulcanization accelerator CBS and application thereof | |
| CN219620890U (en) | Extraction crystallization device of wet-process phosphoric acid | |
| CN220767116U (en) | System for retrieve aluminium iron in follow ternary black powder lixivium | |
| CN118206155B (en) | Method for recovering molybdenum and copper sulfide from molybdenum calcine pickling wastewater to improve purity | |
| CN219897129U (en) | Wet phosphoric acid purifying device | |
| CN116675238A (en) | Method for preparing battery grade lithium carbonate by foam flotation and purification of crude lithium carbonate | |
| CN118724028A (en) | Method for preparing lithium carbonate by using lepidolite | |
| CN118791184A (en) | Column washing water treatment method in potassium phytate production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |