CN115108569B - Method for recovering lithium hydroxide, sodium fluoride and potassium fluoride by using tungsten-tin tailings - Google Patents
Method for recovering lithium hydroxide, sodium fluoride and potassium fluoride by using tungsten-tin tailings Download PDFInfo
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- CN115108569B CN115108569B CN202210944482.0A CN202210944482A CN115108569B CN 115108569 B CN115108569 B CN 115108569B CN 202210944482 A CN202210944482 A CN 202210944482A CN 115108569 B CN115108569 B CN 115108569B
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Abstract
The invention discloses a method for recovering lithium hydroxide sodium fluoride and potassium fluoride by utilizing tungsten tin tailings, which comprises the following steps: s1, ball-milling tungsten-tin tailings; s2, roasting by concentrated sulfuric acid; s3, adding water for primary filtration; s4, adding alkali, stirring the filtrate and filtering for the second time; s5, adding alcohol, stirring and filtering secondary filtrate; s6, adding HF gas, stirring and filtering; s7, adding water for high-temperature crystallization; and S8, crystallizing at low temperature. According to the characteristics of high metal content, especially high tin content, and high alkali metal content in the tungsten tin tailings, the extraction scheme is designed in a targeted manner, the influence of tin on the subsequent alkali metal extraction is effectively eliminated, lithium hydroxide, sodium fluoride and potassium fluoride are respectively obtained, the lithium resource recovery rate is improved, and the waste is reduced.
Description
Technical Field
The invention relates to the field of mine resource recovery, in particular to the field of fluorite tailing recovery.
Background
With the development of the new energy industry of China, the scale of a lithium battery is increased day by day, the requirements for upstream raw materials such as lithium hydroxide, lithium carbonate, lithium fluoride and the like are enlarged day by day, the existing lithium ore resources cannot meet the demand of the lithium resources which are increased at a high speed, but a large amount of lithium residues still exist in the tailings in the existing lithium ore lithium extraction process, and how to formulate a targeted recovery process is the key for solving the problem of the shortage of the lithium resources.
Disclosure of Invention
In order to solve the problems in the prior art, the application discloses a method for recovering lithium hydroxide, sodium fluoride and potassium fluoride by using tungsten tin tailings, which comprises the following steps:
s1, ball-milling tungsten-tin tailings, mixing the tungsten-tin tailings, sulfate and a sucrose calcium solution, and carrying out wet ball milling;
step S2, roasting by concentrated sulfuric acid, namely roasting the mixed slurry obtained in the step S1 and the concentrated sulfuric acid together;
step S3, adding water for primary filtration, adding the powder calcined by the concentrated sulfuric acid obtained in the step S2 into the water, stirring and filtering to obtain filtrate and filter residues;
step S4, adding alkali, stirring filtrate and carrying out secondary filtration, adding a sodium hydroxide solution into the filtrate obtained in the step S3, stirring to obtain a mixed liquid, and carrying out secondary filtration on the mixed liquid to obtain hydroxide precipitate and secondary filtrate;
step S5, adding alcohol, stirring and filtering secondary filtrate, adding the secondary filtrate obtained in the step S4 into ethanol, stirring and filtering to obtain lithium hydroxide precipitate and alkali metal hydroxide alcohol solution;
step S6, adding HF gas, stirring and filtering, introducing hydrogen fluoride gas into the alkali metal hydroxide alcoholic solution obtained in the step S5, stirring and filtering to obtain filtrate and filter residues, wherein the filter residues comprise potassium fluoride and sodium fluoride;
s7, adding water for high-temperature crystallization, adding excessive water into the filter residue obtained in the step S6 to completely dissolve the filter residue, evaporating and crystallizing at the temperature of more than 80 ℃, stopping high-temperature crystallization after the sodium fluoride crystal is produced and before the potassium fluoride is separated out, and filtering and collecting the sodium fluoride crystal and the filtrate containing the potassium fluoride;
and S8, crystallizing at low temperature, namely performing evaporation crystallization on the filtrate obtained in the step S7 at 10 ℃ to obtain potassium fluoride crystals.
And performing wet ball milling on the tungsten-tin tailings in advance before mixing the tungsten-tin tailings, the sulfate and the sucrose calcium solution for wet ball milling.
In the step S1, the sulfate includes sodium sulfate and calcium sulfate; and the mass percentage of water in the mixed slurry obtained by the wet ball milling in the step S1 is not more than 10%.
In the step S2, the used concentrated sulfuric acid is 98% by mass, the roasting temperature is 700 to 1000 ℃, and the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: and adding the concentrated sulfuric acid into the mixed slurry for multiple times, and continuously stirring.
The roasting process of the step S2 is carried out in a roasting furnace, the roasting furnace is provided with a pure water inlet, a mixed liquid outlet and a stirring device, in the step S3, after the roasting process is finished, pure water is introduced into the roasting furnace through the pure water inlet, the stirring device is started at the same time, and after the mixed roasted powder and the pure water are stirred to form a mixed liquid, the mixed liquid is discharged to a continuous filtering device through the mixed liquid outlet to obtain filtrate and filter residues; continuous filter equipment is including removing the filter screen, and drive arrangement mixed liquid outlet discharge the in-process of mixed liquid, the filter residue is filtered extremely remove the filter screen top, drive arrangement drives remove the filter screen continuation and take away the filter residue.
In the step S4, the sodium hydroxide solution is added until no precipitate is generated, and the pH range of the stirred mixed liquid is 8-9.
In the step S4, the adding process of the sodium hydroxide solution is successive adding, and when the PH of the sodium hydroxide solution added to the mixed solution is 7, the PH of the mixed solution is measured after stirring and mixing are required after each subsequent addition of the sodium hydroxide solution; after the sodium hydroxide solution is added to the mixed solution with the pH value of 7, the sodium hydroxide solution added each time can not increase the pH value of the mixed solution to be more than 1; and when the sodium hydroxide solution is added until no precipitate is generated, and the pH range in the stirred mixed liquid is 8-9, adding 10-50ml of dilute sulfuric acid solution with the concentration of 3-5mol/L, and observing whether the precipitate is produced or not.
And in the step S5, adding ethanol until no precipitate is generated, and filtering to obtain potassium fluoride and sodium fluoride precipitates.
In the step S6, introducing the hydrogen fluoride gas into the alkali metal hydroxide alcoholic solution until no precipitate is generated;
s6, adopting a continuous filtering device in the filtering process to obtain filtrate and filter residues; the continuous filtering device comprises a movable filter screen and a driving device, filter residues are filtered to the position above the movable filter screen, and the driving device drives the movable filter screen to continuously take away the filter residues;
in the step S6, the pH range of the filtrate is 7-8, and when the pH of the filtrate is less than 7, a sodium hydroxide solution needs to be added.
In the step S7 and the step S8, the total mass M0 of the filter residue containing potassium fluoride and sodium fluoride obtained in the step S6 is measured in advance, and the potassium fluoride having a dissolved mass M0 is calculated from the solubility of potassium fluoride at 80 ℃, corresponding to the mass Mk of water used, and converted into the volume Vk of corresponding water;
calculating the mass Mn of the sodium fluoride with the dissolved mass M0 according to the solubility of the sodium fluoride at 80 ℃, and converting the mass Mn into the volume Vn of the corresponding water;
adding water into the potassium fluoride and sodium fluoride precipitate obtained in the step S6 until the precipitate is completely dissolved to form a uniform solution, then evaporating and crystallizing at 80 ℃ until the volume of the residual water in the solution is Vk', and simultaneously filtering to obtain sodium fluoride crystals and a filtrate after high-temperature crystallization;
cooling the filtrate after high-temperature crystallization to 10 ℃, and evaporating and crystallizing to obtain potassium fluoride crystals;
wherein Vk < Vk' < 2Vk is characterized in that,
and in the evaporation crystallization process at 80 ℃ in the step S7, a multi-time filtering mode is adopted, and after the final filtering is finished and the high-temperature crystallization is finished, the cooling process is started.
The method disclosed by the invention has the following advantages:
according to the method, the extraction scheme is designed in a targeted manner according to the characteristics of high metal content, especially high tin content, and high alkali metal content in the tungsten-tin tailings, so that the influence of tin on the subsequent alkali metal extraction is effectively eliminated, lithium hydroxide, sodium fluoride and potassium fluoride are obtained respectively, the lithium resource recovery rate is improved, and the waste is reduced.
Description of the drawings:
in order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a schematic diagram of the steps of recovering sodium lithium hydroxide fluoride and potassium fluoride from tungsten tin tailings.
Detailed Description
The following will be clearly and completely described in conjunction with the technical solutions of the embodiments of the present application;
the tungsten-tin tailings contain a large amount of metals, and in the process of extracting alkali metal resources, the common method is to produce precipitates such as hydroxides, fluorides and the like of the alkali metals by a precipitation method to sequentially extract the alkali metals; however, the hydroxide of tin has two sides, and can form a precipitate in an alkali solution to influence the precipitation of the hydroxide of alkali metal, and can also be dissolved in an excessive alkali solution; while lithium hydroxide is soluble in water but insoluble in ethanol; the potassium hydroxide and the sodium hydroxide are dissolved in water and ethanol, and the lithium hydroxide in the alkali metal hydroxide can be separated by the ethanol; the potassium fluoride and sodium fluoride are soluble in water but insoluble in ethanol, and can be extracted with ethanol; then, potassium fluoride and sodium fluoride can be crystallized and separated at different temperatures according to the great difference of the melting points of the potassium fluoride and the sodium fluoride; however, tin fluoride is also insoluble in ethanol, and it is important how to remove the interference of tin in advance in the process of separating lithium hydroxide, potassium fluoride and sodium fluoride by ethanol. According to the method for recovering the lithium hydroxide, the sodium fluoride and the potassium fluoride, which is designed according to the tungsten tin tailings, tin interference is avoided, and meanwhile, the recovery rate of alkali metals in the tungsten tin tailings can be improved;
as shown in the figure 1 of the drawings,
the application discloses a method for recovering lithium hydroxide sodium fluoride and potassium fluoride by utilizing tungsten tin tailings, which comprises the following steps:
s1, ball-milling tungsten-tin tailings, mixing the tungsten-tin tailings, sulfate and a sucrose calcium solution, and carrying out wet ball milling; the sulfate here serves to provide a sufficient amount of sulfate to facilitate the subsequent sulfuric acid roasting process, while calcium sucrose decomposes to calcium oxide at about 200 degrees celsius during the subsequent roasting process, which can help reduce caking in the mixed slurry. So select for use sulfate, the calcium sucrose and the fluorite tailing of solution state to mix because the solution state helps the misce bene, and because the calcium sucrose dissolves in water, compares other calcium salt forms such as direct mixed calcium oxide or calcium carbonate, can more help weakening the caking reaction, does benefit to the intensive mixing. And because the subsequent roasting process is carried out, excessive water reacts with concentrated sulfuric acid to release a large amount of heat, so that the roasting reaction is not uniform, and the subsequent mixing and lithium extraction processes are influenced, the water content in the sulfate and calcium sucrose solution is strictly controlled.
Step S2, roasting by concentrated sulfuric acid, namely roasting the mixed slurry obtained in the step S1 and the concentrated sulfuric acid together;
step S3, adding water for primary filtration, adding the powder calcined by the concentrated sulfuric acid in the step S2 into the water, stirring and filtering to obtain filtrate and filter residues; note that water may not be added to the powder, otherwise severe splatter reactions may form.
Step S4, adding alkali, stirring filtrate and carrying out secondary filtration, adding a sodium hydroxide solution into the filtrate obtained in the step S3, stirring to obtain a mixed liquid, and carrying out secondary filtration on the mixed liquid to obtain hydroxide precipitate and secondary filtrate;
step S5, adding alcohol, stirring and filtering secondary filtrate, adding ethanol into the secondary filtrate obtained in the step S4, stirring and filtering to obtain lithium hydroxide precipitate and alkali metal hydroxide alcohol solution; the 98% ethanol used here was added in excess in order to facilitate rapid precipitation of more lithium hydroxide.
Step S6, adding HF gas, stirring and filtering, introducing hydrogen fluoride gas into the alkali metal hydroxide alcohol solution obtained in the step S5, stirring and filtering to obtain filtrate and filter residues, wherein the filter residues comprise potassium fluoride and sodium fluoride;
s7, adding water for high-temperature crystallization, adding excessive water into the filter residue obtained in the step S6 to completely dissolve the filter residue, evaporating and crystallizing at the temperature of more than 80 ℃, stopping high-temperature crystallization after the sodium fluoride crystal is produced and before the potassium fluoride is separated out, and filtering and collecting the sodium fluoride crystal and the filtrate containing the potassium fluoride;
and S8, crystallizing at low temperature, namely performing evaporation crystallization on the filtrate obtained in the step S7 at 10 ℃ to obtain potassium fluoride crystals.
The selection of evaporative crystallization above 80 ℃ and low temperature crystallization at 10 ℃ takes into account the solubility of potassium fluoride and sodium fluoride in water;
as shown in the following table:
and performing wet ball milling on the tungsten-tin tailings in advance before mixing the tungsten-tin tailings, the sulfate and the sucrose calcium solution for wet ball milling.
In the step S1, the sulfate includes sodium sulfate and calcium sulfate; and the mass percentage of water in the mixed slurry obtained by the wet ball milling in the step S1 is not more than 10%. Because the subsequent steps involve concentrated sulfuric acid, if the water content exceeds 10%, the dilution of the concentrated sulfuric acid is enhanced, so that the roasting process is influenced, and meanwhile, a large amount of water causes a large amount of heat release in the contact process with the concentrated sulfuric acid, so that the roasting process is uncontrollable, and the roasting reaction is not uniform.
In the step S2, the used concentrated sulfuric acid is 98% by mass, the roasting temperature is 700-1000 ℃, and the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: adding the concentrated sulfuric acid into the mixed slurry for multiple times, and continuously stirring; the roasting process in the step S2. The mixing mode can reduce the influence of heat released after the concentrated sulfuric acid reacts with water, otherwise, the slurry can be splashed everywhere, and safety accidents are caused.
The roasting process in the step S2 is carried out in a roasting furnace, the roasting furnace is provided with a pure water inlet, a mixed liquid outlet and a stirring device, in the step S3, after the roasting process is finished, pure water is introduced into the roasting furnace through the pure water inlet, the stirring device is started, mixed powder and pure water after roasting are stirred to form a mixed liquid, and the mixed liquid is discharged to a continuous filtering device through the mixed liquid outlet, so that filtrate and filter residue are obtained; continuous filter equipment is including removing the filter screen, and drive arrangement mixed liquid outlet discharge the in-process of mixed liquid, the filter residue is filtered extremely remove the filter screen top, drive arrangement drives remove the filter screen continuation and take away the filter residue.
In the step S4, the sodium hydroxide solution is added until no precipitate is generated, and the pH range of the stirred mixed liquid is 8-9.
In the step S4, the adding process of the sodium hydroxide solution is successive adding, and when the PH of the sodium hydroxide solution added to the mixed solution is 7, the PH of the mixed solution is measured after stirring and mixing are required after each subsequent addition of the sodium hydroxide solution; after the sodium hydroxide solution is added to the mixed solution with the pH of 7, the pH of the mixed solution cannot be increased by more than 1 by the sodium hydroxide solution added each time; and when the sodium hydroxide solution is added until no precipitate is generated, and the pH range in the stirred mixed liquid is 8-9, adding 10-50ml of dilute sulfuric acid solution with the concentration of 3-5mol/L, and observing whether the precipitate is produced or not.
And in the step S5, adding ethanol until no precipitate is generated, and filtering to obtain potassium fluoride and sodium fluoride precipitates.
In the step S6, introducing the hydrogen fluoride gas into the alkali metal hydroxide alcoholic solution until no precipitate is generated;
s6, adopting a continuous filtering device in the filtering process to obtain filtrate and filter residues; the continuous filtering device comprises a movable filter screen and a driving device, filter residues are filtered to the position above the movable filter screen, and the driving device drives the movable filter screen to continuously take away the filter residues;
in the step S6, the pH range of the filtrate is 7-8, and when the pH of the filtrate is less than 7, a sodium hydroxide solution needs to be added.
In the step S7 and the step S8, the total mass M0 of the filter residue including potassium fluoride and sodium fluoride obtained in the step S6 is measured in advance, potassium fluoride having a dissolved mass M0 is calculated from the solubility of potassium fluoride at 80 ℃, and the mass Mk of water used is corresponded to, and converted into the volume Vk of the corresponded water;
calculating sodium fluoride with the dissolving mass M0 according to the solubility of the sodium fluoride at 80 ℃, corresponding to the mass Mn of the used water, and converting the mass Mn into the volume Vn of the corresponding water;
adding water into the potassium fluoride and sodium fluoride precipitate obtained in the step S6 until the precipitate is completely dissolved to form a uniform solution, then evaporating and crystallizing at 80 ℃ until the volume of the residual water in the solution is Vk', and simultaneously filtering to obtain sodium fluoride crystals and a filtrate after high-temperature crystallization;
cooling the filtrate after high-temperature crystallization to 10 ℃, and evaporating and crystallizing to obtain potassium fluoride crystals;
wherein Vk < Vk ' < 2Vk, where Vn > Vk is known from the solubility of sodium fluoride and potassium fluoride, sodium fluoride begins to precipitate only when the water content in the solution falls below Vn, and potassium fluoride begins to precipitate only when the remaining volume in the solution is below Vk, so that sodium fluoride will precipitate when the remaining water content in the solution is between Vn and Vk, but considering that the precipitated crystals will occupy a portion of the volume and the density of the salt solution is higher than that of the aqueous solution, it is selected to terminate the precipitation of sodium fluoride when Vk ' is greater than Vk, and for more sodium fluoride precipitation, it is preferred that Vk ' is not greater than 2 Vk.
In the 80 ℃ evaporative crystallization process of the step S7, a multi-time filtration mode is adopted, and after the last filtration is finished and the cooling process is started, the last filtration is carried out. Sodium fluoride crystals are filtered for many times, which is beneficial to reducing the influence of the crystal volume on the observation of the volume of the aqueous solution.
The method disclosed by the invention has the following advantages:
according to the characteristics of high metal content, especially high tin content, and high alkali metal content in the tungsten tin tailings, the extraction scheme is designed in a targeted manner, the influence of tin on the subsequent alkali metal extraction is effectively eliminated, lithium hydroxide, sodium fluoride and potassium fluoride are respectively obtained, the lithium resource recovery rate is improved, and the waste is reduced.
Claims (9)
1. A method for recovering lithium hydroxide, sodium fluoride and potassium fluoride by utilizing tungsten tin tailings is characterized by comprising the following steps:
s1, ball-milling tungsten-tin tailings, mixing the tungsten-tin tailings, sulfate and a sucrose calcium solution, and carrying out wet ball milling;
step S2, roasting by concentrated sulfuric acid, namely roasting the mixed slurry obtained in the step S1 and the concentrated sulfuric acid together;
step S3, adding water for primary filtration, adding the powder calcined by the concentrated sulfuric acid in the step S2 into the water, stirring and filtering to obtain filtrate and filter residues;
step S4, adding alkali, stirring filtrate and carrying out secondary filtration, adding a sodium hydroxide solution into the filtrate obtained in the step S3, stirring to obtain a mixed liquid, and carrying out secondary filtration on the mixed liquid to obtain a hydroxide precipitate and a secondary filtrate;
step S5, adding alcohol, stirring and filtering secondary filtrate, adding the secondary filtrate obtained in the step S4 into ethanol, stirring and filtering to obtain lithium hydroxide precipitate and an alkali metal hydroxide alcohol solution;
step S6, adding HF gas, stirring and filtering, introducing hydrogen fluoride gas into the alkali metal hydroxide alcoholic solution obtained in the step S5, stirring and filtering to obtain filtrate and filter residues, wherein the filter residues comprise potassium fluoride and sodium fluoride;
s7, adding water for high-temperature crystallization, adding excessive water into the filter residue obtained in the step S6 to completely dissolve the filter residue, then evaporating and crystallizing at the temperature of more than 80 ℃, stopping high-temperature crystallization after the production of sodium fluoride crystals and before the precipitation of potassium fluoride, and filtering and collecting the sodium fluoride crystals and the filtrate containing potassium fluoride;
s8, crystallizing at low temperature, namely performing evaporation crystallization at 10 ℃ on the filtrate obtained in the step S7 to obtain potassium fluoride crystals; in the step S7, the total mass M0 of the residue containing potassium fluoride and sodium fluoride obtained in the step S6 is measured in advance, potassium fluoride having a dissolved mass M0 is calculated from the solubility of potassium fluoride at 80 ℃, and the mass Mk of water used is corresponded to, and converted into the volume Vk of the corresponded water;
calculating sodium fluoride with the dissolving mass M0 according to the solubility of the sodium fluoride at 80 ℃, corresponding to the mass Mn of the used water, and converting the mass Mn into the volume Vn of the corresponding water;
adding water into the potassium fluoride and sodium fluoride precipitate obtained in the step S6 until the precipitate is completely dissolved to form a uniform solution, then evaporating and crystallizing at 80 ℃ until the volume of the residual water in the solution is Vk', and simultaneously filtering to obtain sodium fluoride crystals and a filtrate after high-temperature crystallization;
cooling the filtrate after high-temperature crystallization to 10 ℃, and evaporating and crystallizing to obtain potassium fluoride crystals;
wherein Vk < Vk' < 2Vk,
in the 80 ℃ evaporative crystallization process of the step S7, a multi-time filtration mode is adopted, and after the last filtration is finished and the cooling process is started, the last filtration is carried out.
2. The method for recycling sodium fluoride and potassium fluoride with tungsten tin tailings as claimed in claim 1, wherein the tungsten tin tailings are subjected to wet ball milling in advance before the tungsten tin tailings, the sulfate and the sucrose calcium solution are mixed and subjected to wet ball milling.
3. The method for recycling sodium fluoride and potassium fluoride with tungsten-tin tailings according to claim 2, wherein in the step S1, the sulfate comprises sodium sulfate and calcium sulfate; and the mass percentage of water in the mixed slurry obtained by the wet ball milling in the step S1 is not more than 10%.
4. The method for recycling lithium hydroxide, sodium fluoride and potassium fluoride by using tungsten tin tailings according to claim 3, wherein the concentrated sulfuric acid used in the step S2 is 98% by mass, the roasting temperature is 700-1000 ℃, and the mixing sequence of the mixed slurry and the concentrated sulfuric acid is as follows: and adding the concentrated sulfuric acid into the mixed slurry for multiple times, and continuously stirring.
5. The method for recycling lithium fluoride and potassium fluoride from tungsten-tin tailings according to claim 4, wherein the roasting process in the step S2 is performed in a roasting furnace, the roasting furnace is provided with a pure water inlet, a mixed liquid outlet and a stirring device, in the step S3, after the roasting process is completed, pure water is introduced into the roasting furnace through the pure water inlet, the stirring device is started, and after mixed liquid is formed by stirring and mixing roasted powder and pure water, the mixed liquid is discharged to a continuous filtering device through the mixed liquid outlet to obtain filtrate and filter residue; continuous filter equipment is including removing the filter screen, and drive arrangement mixed liquid outlet discharge the in-process of mixed liquid, the filter residue is filtered extremely remove the filter screen top, drive arrangement drives remove the filter screen continuation and take away the filter residue.
6. The method for recycling sodium fluoride and potassium fluoride with tungsten-tin tailings as recited in claim 5, wherein in the step S4, the sodium hydroxide solution is added until no precipitate is formed, and the pH value of the stirred mixed liquid is in a range of 8-9.
7. The method for recycling lithium fluoride and potassium fluoride from tungsten tin tailings as recited in claim 6, wherein in the step S4, the sodium hydroxide solution is added sequentially, and when the PH of the sodium hydroxide solution added to the mixed solution is 7, the PH of the mixed solution is measured after stirring and mixing are required after each subsequent addition of the sodium hydroxide solution; after the sodium hydroxide solution is added to the mixed solution with the pH value of 7, the sodium hydroxide solution added each time can not increase the pH value of the mixed solution to be more than 1; and when the sodium hydroxide solution is added until no precipitate is generated, and the pH range in the stirred mixed liquid is 8-9, adding 10-50ml of dilute sulfuric acid solution with the concentration of 3-5mol/L, and observing whether the precipitate is produced or not.
8. The method for recycling lithium fluoride and potassium fluoride from tungsten tin tailings as claimed in claim 7, wherein the step S5 comprises adding ethanol until no precipitate is formed, and filtering to obtain potassium fluoride and sodium fluoride precipitate.
9. The method for recycling lithium fluoride and potassium fluoride from tungsten tin tailings according to claim 8, wherein in the step S6, the hydrogen fluoride gas is introduced into the alkali metal hydroxide alcoholic solution until no precipitate is formed;
s6, adopting a continuous filtering device in the filtering process to obtain filtrate and filter residues; the continuous filtering device comprises a movable filter screen and a driving device, filter residues are filtered to the position above the movable filter screen, and the driving device drives the movable filter screen to continuously take away the filter residues;
in the step S6, the PH range of the filtrate is 7-8, and when the PH of the filtrate is less than 7, a sodium hydroxide solution needs to be added;
and a hydrogen fluoride gas recovery device is not additionally arranged in the step S6.
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| CN107999271A (en) * | 2017-11-17 | 2018-05-08 | 北京有色金属研究总院 | A kind of method from APT Tungsten smeltings slag for comprehensive recycling useful metal |
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