CN110550644A - method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite - Google Patents
method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite Download PDFInfo
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- C01D15/08—Carbonates; Bicarbonates
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D17/00—Rubidium, caesium or francium compounds
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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Abstract
The invention provides a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which takes the lepidolite as a raw material and adopts an acidification roasting method, wherein the acidification roasting method comprises the steps of crushing, feeding and pulping, acidification leaching, stirring, drying, acidification roasting, water leaching reaction, twice cooling and crystallization, adding alkali to neutralize and separate gypsum solid slag, adding an impurity removing agent to remove impurities, evaporating and concentrating, preparing crude lithium carbonate, rubidium, cesium and vanadium salt and the like, so that the comprehensive cost of lepidolite extraction is greatly reduced, and the comprehensive competitiveness of lepidolite extraction is greatly improved; the method for preparing the battery-grade lithium carbonate, rubidium and cesium salt has the advantages of high equipment utilization rate, small discharge of three environmental-friendly wastes and low production cost.
Description
The technical field is as follows: the invention relates to an extraction method for separating and extracting refined lithium carbonate and rubidium and cesium from a lepidolite raw material, in particular to a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite.
Background art:
The lithium battery new energy is one of national key support and development energy industries; lithium carbonate is used as an important basic raw material for the development of new energy of lithium batteries, and the production and demand of the lithium carbonate are increasingly large, and the price of the lithium carbonate is also increasingly high.
Lepidolite is an important mineral resource and contains abundant rare metal materials, lithium, sodium, potassium, rubidium, cesium, aluminum and the like. With the increasing shortage of world energy, developing and utilizing new energy is a common topic in the world and is more and more emphasized by various countries; lithium and salts thereof such as lithium carbonate and lithium sulfate are basic raw material products of the lithium new energy industry, and since lepidolite contains lithium metal which is a basic material of the lithium new energy industry, the development and application of lepidolite become a popular problem at present.
china has the largest tantalum-niobium-lithium ore in Asia at present, the tantalum-niobium-lithium resource is rich, the content of lithium dioxide in lepidolite reaches 4.5 percent, and the method has the advantage condition of extracting lithium carbonate resource. Meanwhile, the lithium mica powder also contains abundant rubidium, cesium, potassium and other resources, so that the lithium carbonate, the rubidium, the cesium, the potassium and the like are extracted by taking the lepidolite as a raw material, and the lithium mica powder has a wide market prospect and good economic benefits.
from the existing production process, the comprehensive extraction of resources such as lithium carbonate, rubidium, cesium and potassium is not ideal, the comprehensive production benefit is not high, the input-output ratio is insufficient, and the industrial production is difficult to realize. How to realize the technical production of the lepidolite all-element separation and extraction process, and the other process technologies only can implement the production to lithium carbonate, a mixture and the like, how to realize the essential promotion of the technical process, how to realize the all-element industrialized extraction of lithium, rubidium, cesium and potassium in the lepidolite concentrate, realize the full resource utilization, and have great economic benefit and deep environmental benefit: firstly, how to realize the separation and extraction of high-purity rubidium salt and cesium salt by 1 time of tailings generated after lithium extraction can bring high additional economic benefit, greatly reduce the comprehensive cost of lepidolite extraction and greatly improve the comprehensive competitiveness of lepidolite extraction;
secondly, how to realize the actual utilization of rubidium and cesium in the lepidolite raw material, thereby realizing the separation, extraction and utilization of the downstream rubidium and cesium of the secondary tailings for separating and extracting potassium; thirdly, only by separating lithium, rubidium, cesium and potassium in the lepidolite and utilizing all resources, the environment-friendly discharge of 0 can be realized in the true sense of the lepidolite raw material, and the comprehensive development, utilization and development of the lepidolite raw material ore are promoted; reducing the large pressure on the environment.
The invention content is as follows:
the invention provides a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which takes the lepidolite as a raw material and adopts an acidification roasting method, wherein the acidification roasting method comprises the steps of crushing, feeding and pulping, acidification leaching, stirring, drying, acidification roasting, water leaching reaction, twice cooling and crystallization, adding alkali to neutralize and separate gypsum solid slag, adding an impurity removing agent to remove impurities, evaporating and concentrating, preparing crude lithium carbonate, rubidium, cesium and vanadium salt and the like, so that the comprehensive cost of lepidolite extraction is greatly reduced, and the comprehensive competitiveness of lepidolite extraction is greatly improved; the method for preparing the battery-grade lithium carbonate, rubidium and cesium salt has the advantages of high equipment utilization rate, small discharge of three environmental-friendly wastes and low production cost.
the invention discloses a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which uses the lepidolite as a raw material, adopts multiple circulation modes of acidification roasting, leachate circulation and lithium extraction mother liquor circulation, controls the concentration of potassium, sodium, rubidium and cesium in the mother liquor corresponding to each working procedure, and adopts a method of combination of evaporation concentration and crystal phase, and the method specifically comprises the following steps:
1) crushing, adding materials and pulping, namely crushing lepidolite into powder, sealing and stacking, and conveying the powder or prepared slurry into a reaction kettle device to obtain pretreated lepidolite powder;
2) Acidifying and leaching, namely adding pretreated lithium mica powder, concentrated sulfuric acid and water into a reaction kettle device together, stirring and mixing uniformly to obtain a lithium mica acid water mixture, heating steam under the normal pressure environment condition for 3-6 hours to obtain sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium, hydrogen fluoride and fluoride generated by an acidifying reaction, acid steam and residual acid, and cooling the sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium to obtain an acidified leaching material; hydrogen fluoride and fluoride generated by the acidification reaction and acid steam enter a tail gas recovery treatment system for treatment; neutralizing and filter-pressing the hydrogen fluoride and fluoride generated by the acidification reaction, acid steam and residual acid to obtain filtrate and filter residue 1, returning the filtrate to the water supplementing process of the acidification leaching process, and recycling or externally selling the filter residue 1;
3) mixing and drying, namely adding water into the acidified leaching material obtained in the step 2) to prepare acidified leaching mixed solution, adding dried silica sand into the acidified leaching mixed solution, mixing and continuously stirring to prepare solid-liquid mixed solution, fully stirring and mixing the solid-liquid mixed solution, and then placing the solid-liquid mixed solution into a drying device for drying to obtain dried mixed material; the water vapor and tail gas generated during drying are treated by a tail gas recovery treatment system and sprayed and then discharged after reaching the standard;
4) Acidizing and roasting, namely placing the dried and mixed material obtained in the step 3) into a roasting kiln for roasting treatment, and controlling the roasting treatment temperature to be 300-900 ℃ to obtain a roasted material; after waste gas generated by roasting enters a tail gas recovery treatment system for treatment, the waste gas is discharged after reaching the standard;
5) Water leaching reaction, namely adding water into the roasted material obtained in the step 4), stirring and mixing to obtain solid-liquid mixture, and controlling the solid-liquid mass ratio of the roasted material to the water to be 1: 1.1-1.3, carrying out water leaching treatment to obtain a solid-liquid mixed water solution, filtering and separating the solid-liquid mixed water solution after the water leaching treatment is finished to obtain a mother solution 2 and a filter residue 2, washing the filter residue 2 and drying to obtain dry silica sand;
6) primary cooling crystallization, namely placing the mother liquor 1 and the mother liquor 2 in a cooling crystallization device, and adopting circulating frozen brine for cooling treatment to obtain primary cooling crystallization under the condition of continuous stirring to obtain a mixed solution of precipitated aluminum rubidium alum and aluminum cesium alum; filtering and separating the mixed solution of aluminum, rubidium, alum and aluminum, cesium and alum to obtain a mother solution 3, a rubidium, cesium and alum mixture and a rubidium, cesium and potassium mixture of potassium, sodium and alum;
7) performing secondary cooling crystallization to prepare potassium sodium alum, adding a secondary catalytic crystallization agent into the mother liquor 3 obtained in the step 6), performing cooling secondary cooling crystallization treatment to obtain a mixed solution of aluminum sodium alum and aluminum potassium alum, and filtering and separating the mixed solution of aluminum sodium alum and aluminum potassium alum to obtain a mother liquor 4 and potassium sodium alum;
8) adding alkali to neutralize and separate gypsum solid residue, adding lime milk into the mother liquor 4 obtained in the step 7), then adding hydrogen peroxide solution to obtain a mother liquor mixed solution, generating a large amount of precipitates by controlling the pH value of the mother liquor mixed solution, and performing filter pressing and separation to obtain gypsum solid residue and a mother liquor 5;
9) adding an impurity removal catalyst to remove impurities, adding the impurity removal catalyst into the mother liquor 5 obtained in the step 8) to remove impurities, filtering and separating to obtain solid gypsum residues and a mother liquor 6; returning the gypsum solid slag to the step 2), wherein the neutralization process is a neutralization addition raw material;
10) Evaporating and concentrating, namely putting the mother liquor 6 into an MVR high-efficiency evaporator, performing high-temperature evaporating and concentrating treatment to obtain an evaporated and concentrated solution, controlling the concentration of Li ions in the evaporated and concentrated solution to be 14-33g/L to obtain a concentrated mother liquor 7, and performing lithium precipitation and agitation washing on the concentrated mother liquor 7; recovering the condensed water generated by the high-temperature evaporation and concentration treatment into the washing water for preparing the sodium carbonate and the lithium carbonate;
11) Separating to prepare crude lithium carbonate, adding carbonate solution into the concentrated solution mother liquor 7, carrying out lithium precipitation reaction, obtaining crude lithium carbonate and mother liquor 8 after lithium precipitation, and washing the crude lithium carbonate by using heated water, wherein the mother liquor 8 after lithium precipitation is evaporated and concentrated by an evaporator until the concentration of Li 2 O in the solution is 15-30g/L, carrying out centrifugal filtration separation to obtain solid and centrifugal separation solution, drying the solid to obtain anhydrous sodium sulfate solid, and carrying out secondary lithium precipitation on the centrifugal separation solution to obtain industrial-grade lithium carbonate which is crude lithium carbonate;
12) Purifying the crude lithium carbonate to prepare battery-grade lithium carbonate, adding water into the crude lithium carbonate, fully stirring and mixing to prepare a crude lithium carbonate mixed aqueous solution, introducing CO 2 gas into the crude lithium carbonate mixed aqueous solution for dissolving, after the crude lithium carbonate is fully dissolved, decomposing under the heating condition, removing impurities, filtering and separating, drying filter residues by a dryer to obtain the battery-grade lithium carbonate, and recovering filtrate;
13) preparing rubidium-cesium salt, namely performing back extraction on the rubidium-cesium-alum prepared in the step 6) and a rubidium-cesium-potassium mixture of potassium-sodium alum by using corresponding acid, and preparing a high-purity cesium salt product and a corresponding raffinate; and performing acid stripping by using the raffinate as a raw material to prepare a high-purity rubidium salt product.
preferably, in the step 2), the acidification leaching is performed, wherein the mass ratio of pretreated lithium mica powder to concentrated sulfuric acid to water is controlled to be 1: 0.8-1.05: 0.8-1.1; controlling the steam heating reaction temperature to be 80-150 ℃; the temperature reduction treatment is to control the temperature of the temperature reduction treatment to be 80-100 ℃; the neutralization is to add lime milk or lime milk made of gypsum solid residue into the residual acid for neutralization treatment, and the pH value of the neutralization treatment is controlled to be 6-9.
Preferably, in the step 3), the material mixing and drying are carried out, wherein the solid-liquid ratio of the solid-liquid mixed solution is controlled to be 0.3: 1-0.5: 1, controlling the drying to be drying by adopting a rotary drying kiln device, controlling the drying time to be 0.4-0.6h and controlling the drying temperature to be 100-150 ℃; and controlling the water vapor generated during drying and the tail gas generated by combustion to enter a tail gas treatment system of the rotary drying kiln, firstly spraying water to prepare dilute sulfuric acid with the concentration of 30-38Wt%, returning the dilute sulfuric acid to the acid leaching process for use, and discharging the sprayed tail gas after the tail gas is subjected to secondary treatment by soda lime absorption to reach the standard.
the method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite comprises the step 5) of water leaching reaction, wherein the time of water leaching treatment is controlled to be 1-3 hours, and the temperature of the water leaching treatment is 70-95 ℃; and (3) returning the silica sand to be used as the raw material in the steps of stirring and drying in the step 3).
The method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite comprises the step 6) of primary cooling crystallization, wherein the temperature of the primary cooling crystallization is controlled to be 10-65 ℃ for crystallization, and the cooling crystallization time is controlled to be 3-6 hours.
the method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite comprises the following steps of 7) carrying out secondary cooling crystallization, wherein the temperature of the secondary cooling crystallization is controlled to be-15-25 ℃, and the time is 3-6 hours; the secondary catalytic crystallization agent is a mixed solution of multiple or all component solutions of aminobutyric acid, hydrochloric acid, liquid ammonia, calcium chloride, magnesium chloride, sodium phosphate and sodium nitrate.
further, adding alkali to neutralize and separate gypsum solid residue in the step 8), namely adding 30-35wt% of lime milk into the mother liquor 4 at the temperature of-15-25 ℃, and then adding 20-30wt% of hydrogen peroxide solution.
preferably, in the step 9), an impurity removing agent is added for removing impurities, wherein the impurity removing agent is a mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and a sodium phosphate solution; the gypsum solid residue obtained by separation is calcium oxide or calcium hydroxide.
further, separating crude lithium carbonate in the step 11), adding a sodium carbonate or potassium carbonate solution into the concentrated solution mother liquor 7, and controlling the reaction temperature of lithium precipitation to be 80-95 ℃; the time is 40-100 minutes.
The invention relates to a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which takes the lepidolite as a raw material and adopts the ten working procedures of crushing, feeding and pulping, acidifying and leaching, stirring, drying, acidifying and roasting, water leaching reaction, cooling and crystallization for two times, adding alkali to neutralize and separate gypsum solid slag, adding an impurity removing agent to remove impurities, evaporating and concentrating, preparing crude lithium carbonate, rubidium and cesium vanadium salt and the like. In the process of extracting battery-grade lithium carbonate, rubidium and cesium salts, wherein in the process of secondary cooling crystallization, a mixed solution of partial or all components of a secondary catalytic crystallization agent, namely aminobutyric acid, hydrochloric acid, liquid ammonia, calcium chloride, magnesium chloride, sodium phosphate and sodium nitrate, is added into the mother liquor 3. The mixed solution of partial components or solutions of a plurality of components refers to the mixed solution of any more than two of the above components in any proportion, or the mixed solution of all the above components in any proportion; the addition proportion of the components of the catalytic crystallization agent is to control the concentration of lithium ions in the mother liquor 4 obtained in the subsequent steps and the removed impurities to meet the extraction conditions and requirements, so that the content of the lithium ions in the prepared mother liquor 4 is improved, the content of the impurities in the solution is further reduced, and the potassium sodium alum can be rapidly crystallized and precipitated. Adding a mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and sodium phosphate solution as an impurity removal catalyst in the impurity removal process; the catalyst does not contain heavy metal salt, and the adding amount of each component of the catalyst is the same as the adding amount of each component of the secondary catalytic crystallization agent; the aim is to remove impurities from the mother liquor 5 more cleanly. The method has the advantages that technical production of the lepidolite all-element separation and extraction process is realized, compared with the prior art, the production can be implemented to a lithium carbonate + rubidium-cesium-potassium mixture, the essential improvement of the technical process is realized, meanwhile, the all-element industrial extraction of lithium, rubidium, cesium and potassium in lepidolite concentrate is realized, the full resource utilization is realized, and the method has great economic benefit and deep environmental benefit, which is mainly reflected in that firstly, high-purity rubidium salt and cesium salt separated and extracted by 1 time of tailings generated after lithium extraction are realized, the high-additional economic benefit can be brought, meanwhile, the comprehensive cost of lepidolite extraction is greatly reduced, and the comprehensive competitiveness of lepidolite extraction is greatly improved; secondly, the practical utilization of rubidium and cesium in the lepidolite raw material is realized, so that the downstream separation, extraction and utilization of rubidium and cesium of the potassium extracted by secondary tailings are realized; thirdly, only lithium, rubidium, cesium and potassium in the lepidolite are separated, full resource utilization is really comprehensive utilization, and waste gas, tail gas and the like enter a recovery treatment system for treatment, namely a tail gas treatment system for treatment and then are discharged, so that environment-friendly 0 discharge is really realized for the lepidolite raw material, and comprehensive extraction, utilization and development of the lepidolite raw material ore are promoted; reducing the pressure on the environment. The lithium content in the leaching solution is greatly improved, and the leaching residue is common solid waste residue because of water leaching, and can be used as a raw material of building materials. Meanwhile, the production method has the advantages of stable operation process, short production period, high equipment utilization rate, low production cost, more raw materials recycling, less three-waste discharge and small influence on environment.
The invention relates to a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite, which adopts a water leaching acidification roasting method, wherein leaching residues are common solid waste residues and can be used as raw materials of building materials, and the production cost is greatly reduced.
The invention discloses a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which mainly comprises the following process flows of lepidolite crushing, pulping → acidification leaching → filtration separation → material mixing drying → acidification roasting → water leaching → filtration → cooling crystallization → filtration separation → secondary cooling crystallization → rubidium, cesium and alum → mother liquor evaporation → impurity removal → lithium carbonate preparation and rubidium and cesium salt preparation.
the purity of the battery-grade lithium carbonate prepared by the method of the invention is over 99.5 percent through the detection of relevant departments, and the quality indexes of the product are shown in the following table 1 through the detection of various relevant technical indexes, and the quality index of the product is shown in the table 1
description of the drawings: 1. the water content in the product is less than or equal to 0.40 percent;
2. the average grain diameter of the product is less than or equal to 6 mu m; d50 is more than or equal to 2 mu m and less than or equal to 4 mu m; d90 is more than or equal to 9 mu m and less than or equal to 12 mu m;
3. the battery grade lithium carbonate is white powder and has no visible impurities.
table 2 shows the quality index of industrial-grade lithium carbonate prepared by the method of the invention,
table 2 quality testing indexes
It shows that most industrial products can reach the general first grade and general second grade, and a small amount of industrial products can reach the general special grade standard.
the quality indexes of the 4N rubidium carbonate product prepared by the method are shown in the following table 3 after detection,
TABLE 3 quality index
Description of the drawings: 1. other 4N rubidium salt chemical compositions refer to 4N rubidium carbonate.
the quality indexes of the 4N cesium carbonate product prepared by the method are shown in the following table 4;
TABLE 4 quality index
Description of the drawings: 1. other 4N cesium salt chemistries were referenced to 4N cesium carbonate.
the specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific examples.
the invention discloses a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite, which takes the lepidolite as a raw material and adopts an acidification roasting method, and comprises the following steps:
1) crushing, adding materials and pulping, namely crushing lepidolite into powder, sealing and stacking, and conveying the powder or prepared slurry into a reaction kettle device to obtain pretreated lepidolite powder;
2) Acidifying and leaching, namely adding pretreated lithium mica powder, concentrated sulfuric acid and water into a reaction kettle device together, stirring and mixing uniformly to obtain a lithium mica acid water mixture, heating steam under the normal pressure environment condition for 3-6 hours to obtain sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium, hydrogen fluoride and fluoride generated by an acidifying reaction, acid steam and residual acid, and cooling the sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium to obtain an acidified leaching material; hydrogen fluoride and fluoride generated by the acidification reaction and acid steam enter a tail gas recovery treatment system for treatment; neutralizing and filter-pressing the residual acid to obtain filtrate and filter residue 1, returning the filtrate to the acidification leaching process for water supplement, and recycling or externally selling the filter residue 1; the mass ratio of the lithium mica powder to the concentrated sulfuric acid to the water is 1: 0.8-1.05: 0.8-1.1; controlling the steam heating reaction temperature to be 80-150 ℃; the temperature reduction treatment is to control the temperature of the temperature reduction treatment to be 80-100 ℃; the neutralization is to add lime milk into the residual acid for neutralization treatment, and the pH value during the neutralization treatment is controlled to be 6-9;
3) stirring and drying, namely adding water and silica sand into the acidified leaching material obtained in the step 2), mixing, continuously stirring to prepare a solid-liquid mixed solution, fully stirring and mixing the solid-liquid mixed solution, and drying in a drying device to obtain a dried stirring material; the water vapor and tail gas generated in drying are treated by a tail gas recovery treatment system and sprayed and then discharged after reaching the standard, and the drying device is a rotary drying kiln for drying; controlling the solid-liquid ratio of the solid-liquid mixed liquid to be 0.3: 1-0.5: 1, controlling the drying to be drying by adopting a rotary drying kiln device, controlling the drying time to be 0.4-0.6h and controlling the drying temperature to be 100-150 ℃;
4) acidizing and roasting, namely placing the dried and mixed material obtained in the step 3) into a roasting kiln for roasting treatment, and controlling the roasting treatment temperature to be 300-900 ℃ to obtain a roasted material; after waste gas generated by roasting enters a tail gas recovery treatment system for treatment, the waste gas is discharged after reaching the standard;
5) performing water leaching reaction, namely adding water into the roasted material obtained in the step 4), stirring and mixing to prepare a solid-liquid mixed solution, and controlling the solid-liquid mass ratio of the roasted material to the water to be 1: 1.1-1.3, carrying out water leaching treatment to obtain a solid-liquid mixed water solution, filtering and separating the solid-liquid mixed water solution after the water leaching treatment is finished to obtain a mother solution 2 and a filter residue 2, washing the filter residue 2 and drying to obtain silica sand; controlling the time of water immersion treatment to be 1-3h, and controlling the temperature of the water immersion treatment to be 70-95 ℃; and (3) returning the silica sand to be used as the raw material in the steps of stirring and drying in the step 3).
6) primary cooling crystallization, namely placing the mother liquor 1 and the mother liquor 2 in a cooling crystallization device, adopting circulating frozen brine for cooling treatment to be primary cooling crystallization under the condition of continuous stirring, controlling the temperature of the primary cooling crystallization to be 10-65 ℃ for crystallization, and controlling the cooling crystallization time to be 3-6 hours; obtaining a mixed solution of aluminum rubidium alum and aluminum cesium alum; filtering and separating the mixed solution of aluminum, rubidium, alum and aluminum, cesium and alum to obtain a mother solution 3, a rubidium, cesium and alum mixture and a rubidium, cesium and potassium mixture of potassium, sodium and alum;
7) secondary cooling crystallization to prepare potassium sodium alum, namely adding a secondary catalytic crystallization agent into the mother liquor 3 obtained in the step 6), and performing cooling secondary cooling crystallization treatment, wherein the temperature of the secondary cooling crystallization is controlled to be-15-25 ℃, and the time is 3-6 hours; the secondary catalytic crystallization agent is a mixed solution of partial or all component solutions of aminobutyric acid, hydrochloric acid, liquid ammonia, calcium chloride, magnesium chloride, sodium phosphate and sodium nitrate; the addition amount and the addition proportion of the components of the secondary catalytic crystallization agent enable the generated alunite and the alunite to be corresponding, enable the concentration of lithium ions in the mother liquor 4 to reach the corresponding quality requirement in the next separation to be corresponding, obtain a mixed solution of the alunite and the alunite, and filter and separate the mixed solution to obtain the mother liquor 4 and the potassium alum;
8) Adding alkali to neutralize and separate gypsum solid residue, adding 30-35wt% of lime milk into the mother liquor 4 in the step 7) at the temperature of-15-25 ℃, and then adding 20-30wt% of hydrogen peroxide solution; obtaining a mother liquor mixed solution, generating a large amount of precipitates by controlling the pH value of the mother liquor mixed solution, and performing filter pressing and separation to obtain gypsum solid residues and a mother liquor 5;
9) adding an impurity removal catalyst to remove impurities, and adding the impurity removal catalyst into the mother liquor 5 obtained in the step 8) to perform impurity removal treatment, wherein the impurity removal catalyst is a mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and a sodium phosphate solution; filtering and separating to obtain solid residues of calcium oxide or calcium hydroxide and mother liquor 6; the addition amount of each component of the mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and sodium phosphate solution of the same impurity removal catalyst corresponds to the concentration of Li ions in the concentrated solution when each component is added for evaporation and concentration;
10) evaporating and concentrating, namely putting the mother liquor 6 into an MVR high-efficiency evaporator, performing high-temperature evaporating and concentrating treatment to obtain an evaporated and concentrated solution, controlling the concentration of Li ions in the evaporated and concentrated solution to be 14-33g/L to obtain a concentrated mother liquor 7, and performing lithium precipitation and agitation washing on the concentrated mother liquor 7; recovering the condensed water generated by the high-temperature evaporation and concentration treatment into the washing water for preparing the sodium carbonate and the lithium carbonate;
11) separating to prepare crude lithium carbonate, adding carbonate solution into the concentrated solution mother liquor 7, carrying out lithium precipitation reaction, obtaining crude lithium carbonate and mother liquor 8 after lithium precipitation, and washing the crude lithium carbonate by using heated water, wherein the mother liquor 8 after lithium precipitation is evaporated and concentrated by an evaporator until the concentration of Li 2 O in the solution is 15-30g/L, carrying out centrifugal filtration separation to obtain solid and centrifugal separation solution, drying the solid to obtain anhydrous sodium sulfate solid, and carrying out secondary lithium precipitation on the centrifugal separation solution to obtain industrial-grade lithium carbonate which is crude lithium carbonate;
12) purifying the crude lithium carbonate to prepare battery-grade lithium carbonate, adding water into the crude lithium carbonate, fully stirring and mixing to prepare a crude lithium carbonate mixed aqueous solution, introducing CO 2 gas into the crude lithium carbonate mixed aqueous solution for dissolving, decomposing under the heating condition after the crude lithium carbonate is fully dissolved, removing impurities, filtering and separating, drying filter residues by a dryer to obtain the battery-grade lithium carbonate, and recovering filtrate;
13) preparing rubidium-cesium salt, namely performing back extraction on the rubidium-cesium-alum prepared in the step 6) and a rubidium-cesium-potassium mixture of potassium-sodium alum by using corresponding acid, and preparing a high-purity cesium salt product and a corresponding raffinate; and performing acid stripping by using the raffinate as a raw material to prepare a high-purity rubidium salt product. The rubidium and cesium salts prepared by the step use corresponding raffinate and acid back extraction by using the existing technical scheme and acid solution.
Example 1
The concentrations in the examples are given by mass, and those in the following examples are not described in the above embodiments.
The preparation method comprises the steps of carrying out controllable directional reconstruction on the lepidolite mineral structure under the condition of variable temperature and normal pressure, and releasing alkali metals (lithium, potassium, sodium, rubidium and cesium) from the lepidolite mineral in the form of soluble salts; the method adopts various circulation modes such as leachate circulation, lithium extraction mother liquor circulation and the like, controls the concentration of potassium, sodium, rubidium and cesium in the mother liquor of each process, and realizes the effective separation and comprehensive utilization of lithium, potassium, sodium, rubidium and cesium through the orderly combination of technologies such as evaporation concentration, crystallization and the like to obtain the products of lithium carbonate, rubidium salt and cesium salt as well as byproducts of silica sand, potassium salt and sodium salt; finally, adding CaO for precipitation, filtering and separating out gypsum by-products; the lithium extraction mother liquor is returned to the process for comprehensive utilization; the specific implementation method and steps are as follows:
1) Crushing, charging and pulping, namely crushing lepidolite into powder, preprocessing the powder into qualified raw materials, stacking the qualified raw materials in a closed or semi-closed raw material workshop, performing closed stacking processing, then preparing the powder or the pulp, transporting the powder or the pulp to a raw material processing and converting workshop by a forklift when in use, and pumping the powder or the pulp into a reaction kettle device by a conveyor belt or a pump after preparing the pulp to obtain preprocessed lepidolite powder;
2) the method comprises the steps of placing pretreated lepidolite powder or refined lepidolite and purchased qualified lepidolite powder and 98% concentrated sulfuric acid and water in a mass ratio of 1: 0.8-1.05: 0.8-1.1 into an acid leaching reaction kettle, controlling the mass ratio of the materials to balance the lepidolite, 98% sulfuric acid and water in a mass ratio of 1: 0.92: 0.86, putting into a reaction kettle device, reacting for 3-6 hours in a heating mode of introducing steam into a jacket at a temperature varying and a normal pressure of 80-150 ℃ to obtain sulfate mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium, cooling to 80-100 ℃, stirring to obtain an acidified leaching material, introducing HF, SiF 4 and sulfuric acid steam generated by leaching or leaching reaction into a tail gas recovery treatment system along with the steam for treatment (the same below), adding materials recovered by the recovery treatment system into lime milk and pH6-9, filter pressing the neutralized recovered slurry to obtain filtrate, introducing the filtrate of the recovery treatment system and the sulfuric acid steam into a gypsum recovery system, and taking filter residue as a water supplementing and recycling the gypsum filter residue into a gypsum plant, and taking the gypsum filter residue as a main cement filter residue and recycling the gypsum filter residue into the gypsum recovery plant;
The main reaction equation is as follows:
MeF·MeOH·Al2O3·3SiO2+4H2SO4+xH2O→Me2 SO4+Al2(SO4)3
+ HF ≠ +3SiO2+ (x +4) H2O (Me is Li, Na, K, Rb, Cs),
[ or 2[ MeF. MeOH. Al2O 3. 3SiO 2. xH2O → K2O. Al2O 3. 4SiO2+ Me' 2O. Al2O 3. 2SiO 2+ 2HF ═ 2xH2O (Me is Li, Na, Rb, Cs) ],
MO + H2SO4 → MSO4+ H2O (M is Mn, Ca, Mg),
m ' 2O3+3H2SO4 → M ' 2(SO4)3+3H2O (M ' is Fe, Al),
4HF+SiO2→SiF4↑+2H2O；
acid leaching tail gas treatment reaction equation:
H2SO4+Ca(OH)2→CaSO4↓+2H2O，
2SiF4+6Ca(OH)2→2CaSiO3+4CaF2↓+6H2O，
CaSiO3+H2O→Ca(OH)2+SiO2，
2HF+Ca(OH)2→CaF2↓+2H2O；
3) stirring and rotary drying: preparing solid-liquid mixed liquor by using the leached materials, namely the materials obtained in the step 2), the acidified leaching materials, the dried silica sand or the dried silica slag and water, wherein the solid-liquid ratio is controlled to be 0.3: 1-0.5: 1, mixing 0.5:1, burning the mixed powder in a rotary drying kiln at the temperature of 100-;
4) the method comprises the following steps of (1) removing sulfuric acid remained in a material, namely a dry mixed material, reducing the consumption of subsequent lime, reducing the loss of lithium in the raw material and improving the leaching rate, correspondingly reducing the production of gypsum, reducing the loss of lithium and improving the recovery rate of lithium, feeding the dried material, namely the dry mixed material, into a roasting kiln for carrying out acidification roasting treatment at the temperature of 900 ℃ under the condition of 300-plus-one temperature to obtain a roasted material, burning hot air generated by petroleum coking by the acidification roasting kiln, feeding SO 3 and HF generated by roasting and tail gas generated by fuel burning into a tail gas recovery treatment system, firstly spraying water to prepare about 35% of dilute sulfuric acid, returning the dilute sulfuric acid to the acid leaching process for use, and carrying out alkali absorption secondary treatment on the sprayed tail gas to reach the standard and discharging;
The reaction equation of the acidification roasting is as follows:
5) and (3) water leaching reaction: adding water into the roasted material, and performing a water leaching process, wherein the solid-to-liquid ratio is controlled to be 1: 1.1-1.3 the solid-to-liquid ratio of the water leaching reaction in the embodiment is 1:1.1, the water leaching time is 1-3h, the leaching temperature is 70-95 ℃, a jacket steam heating mode is adopted, the water leaching is carried out, then filtration and separation are carried out, mother liquor 2 and filter residue 2 are obtained, the filter residue 2 mainly comprises silica sand, the filter residue is washed and then enters a silica sand drying kiln, hot air generated by burning petroleum coke in the silica sand drying kiln is dried, 65% of the dried silica sand returns to the material mixing process, and is sold for 35%; mixing the mother liquor 2 and the mother liquor 1 and entering a primary cooling crystallization process;
6) And primary cooling crystallization: cooling, namely cooling the mother liquor 2 and the mother liquor 1 to 10-65 ℃ by adopting circulating frozen brine under stirring, wherein the cooling time is 3-6 hours, so as to obtain a mixed solution of precipitated aluminum-rubidium-alum and aluminum-cesium-alum; filtering and separating the mixed solution of aluminum, rubidium, alum and aluminum, cesium and alum to obtain a mother solution 3, a rubidium, cesium and alum mixture and a rubidium, cesium and potassium mixture of potassium, sodium and alum; and rubidium cesium alum with some potassium sodium alum entrained therein;
me 2SO 4+ Al2(SO4)3+12H2O → 2MeAl (SO4) 2.12H 2O ↓ (Me is Rb, Cs, K and Na);
7) And secondary cooling crystallization: under the condition of continuously stirring the mother liquor 3, adding a mixed liquor of solutions of secondary catalytic crystallization agents of aminobutyric acid, hydrochloric acid, liquid ammonia, calcium chloride, magnesium chloride, sodium phosphate and sodium nitrate, wherein in the embodiment, the components are mixed and added according to any proportion and do not contain heavy metal salt; and (4) cooling for the second time, wherein the mother liquor 3 is cooled to-15-25 ℃ again for 3-6 hours to obtain the separated mixed liquor of the sodium alum and the potassium alum. Filtering and separating the mixed solution of the Alnatrovanadium and the Alkalite to obtain a mother solution 4 and the Kalium alum. The addition amount of the secondary catalytic crystallization agent is based on the fact that the Alnatriol and the Alkalite in the mother liquor 3 can be quickly crystallized and impurities are removed under the conditions, meanwhile, the mixing of all components of the secondary catalytic crystallization agent can be equal proportion mixing of all components, so that the concentration of Li ions in the mother liquor 4 obtained by filtration is improved, and the concentration of the Li ions in the concentrated solution is ensured to be corresponding to 14-33g/L in the evaporation and concentration step;
me 2SO 4+ Al2(SO4)3+12H2O → 2MeAl (SO4) 2.12H 2O ↓ (Me is K, Na);
8) adding alkali to neutralize and separate gypsum solid slag: under the condition of-15-25 ℃, adding 30-35Wt% of lime milk into mother liquor 4, finally adding 27.5 Wt% of hydrogen peroxide, generating a large amount of precipitates by controlling different pH values of the solution, and separating out gypsum solid residues (mainly comprising gypsum) and mother liquor 5;
Li2SO4+Ca(OH)2+2H2O→2LiOH+CaSO4·2H2O↓，
M ' 2 (SO 4) 3 +3Ca (OH) 2 +6H2O → 3CaSO 4.2H 2O ↓ +2M ' (OH) 3 ↓ (M ' is Fe, Al),
MSO 4 + Ca (OH)2+2H2O → CaSO4 & 2H2O ↓ + M (OH)2 ↓ (M is Mn, Mg),
2HF+Ca(OH)2→CaF2↓+2H2O，
H2SO4+Ca(OH)2→CaSO4·2H2O↓，
H2O2+2Fe2++2H+→2Fe3++2H2O；
9) Adding an impurity removal catalyst to remove impurities, namely removing impurities from mother liquor: adding an impurity removal catalyst into the mother liquor 5 for impurity removal treatment, wherein the impurity removal catalyst is a mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and a sodium phosphate solution; simultaneously, the components in the impurity removal catalyst can be mixed according to any proportion to prepare an impurity removal catalyst mixed solution, the addition amount of the impurity removal catalyst is matched with the cleanness of the impurity ions such as calcium ions in the mother liquor 5 correspondingly, and the solid residue 2 obtained by separation is mainly calcium oxide or calcium hydroxide of the gypsum solid residue; returning the solid gypsum residue after impurity removal to a neutralization process to be used as lime, and taking the mother liquor after impurity removal as mother liquor 6 to enter an evaporation concentration process;
10) and (3) evaporation and concentration: pumping the mother liquor 6 after impurity removal into an MVR high-efficiency evaporator for evaporation and concentration, controlling the concentration of Li in the solution to be 14-33g/L, and performing lithium precipitation and agitation washing on the obtained mother liquor 7; the condensed water is used as water for production links such as filter cloth washing water of a belt machine in an acid leaching process, water for a boiler room, ground equipment washing, sodium carbonate preparation, lithium carbonate washing and the like;
11) And separating a crude lithium carbonate product: adding a sodium carbonate solution into the mother liquor 7 of the concentrated solution, carrying out lithium precipitation reaction at the temperature of 80-95 ℃ for 40-100 minutes, precipitating lithium, and then filtering and separating to obtain a crude lithium carbonate product and a mother liquor 8; washing the lithium carbonate crude product by using the heated condensed water; after lithium precipitation, the mother liquor 8 enters an MVR evaporator again for evaporation concentration, when the concentration of Li2O in the solution of the mother liquor 8 is 15-30g/L, centrifugal filtration separation is carried out to obtain a solid and a centrifugal separation liquid, the solid is dried to obtain an anhydrous sodium sulfate solid, the centrifugal separation liquid enters a secondary lithium precipitation process to prepare industrial-grade lithium carbonate, and the filtered mother liquor returns to the sodium sulfate MVR evaporator again for evaporation concentration for recycling;
2Li2SO4+Na2CO3→Li2CO3↓+Na2SO4，
12) purifying the coarse lithium carbonate to prepare battery-grade lithium carbonate, namely purifying and drying the product: adding pure water into industrial-grade lithium carbonate, namely unqualified battery-grade lithium carbonate prepared, pulping, introducing CO2 for dissolution, decomposing a mother solution obtained after dissolving the industrial-grade lithium carbonate under a heating condition, removing impurities, and returning part of impurities to the mother solution obtained after removing the impurities; sending the qualified battery-grade lithium carbonate to a dryer for drying, and packaging to obtain a battery-grade lithium carbonate product; lithium carbonate preparation reaction equation:
Li2CO3+CO2+H2O＝2LiHCO3，
13) Preparing rubidium-cesium salt, namely performing back extraction on the rubidium-cesium-alum prepared in the step 6) and a rubidium-cesium-potassium mixture of potassium-sodium alum by using corresponding acid to prepare a high-purity cesium salt product and raffinate: the whole combined extraction process has no high-temperature and high-pressure conditions, and is safe and energy-saving. The byproducts of silica sand and aluminum hydroxide are externally sold, and raffinate or waste liquor after 1 time of extraction is used as raw materials for preparing high-purity rubidium salt; in the whole combined extraction process, the combined extraction agent is kept in an endless loop for infinite times, and a high-purity cesium salt product and a corresponding raffinate are prepared firstly; and performing acid stripping by using the raffinate as a raw material to prepare a high-purity rubidium salt product.
and (3) taking 1-time raffinate waste liquid obtained by preparing cesium salt as an extraction liquid raw material for preparing rubidium salt, and carrying out corresponding acid back extraction on the extracted and prepared rubidium salt to obtain a high-purity rubidium salt product: the whole extraction process has no high-temperature and high-pressure conditions, and is safe and energy-saving. The rubidium salt raffinate prepared by extraction is 2 times of raffinate waste liquid, and is used as a raw material for preparing agricultural potassium sulfate. The combined extraction agent in the whole extraction process is circulated for infinite times in a closed loop, and the method is clean and environment-friendly, completes the comprehensive utilization of rubidium resources, and has profound social and economic benefits. The extraction and stripping liquid and process for preparing rubidium and cesium salts can be carried out according to the prior art method. The lithium carbonate and rubidium-cesium salt products prepared by the method in the embodiment meet the detection quality standard requirements. The method of the invention realizes the industrialized extraction of all elements of lithium, rubidium, cesium and potassium from lepidolite and has great economic and social benefits.
It should be noted that: the above technical solutions disclosed in the present invention are not limited thereto; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention,
All of which are intended to be encompassed within the scope of the claims and the specification of the present invention.
Claims (9)
1. a method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salt from lepidolite takes the lepidolite as a raw material, adopts various circulating modes of acidification roasting, leachate circulation and lithium extraction mother liquor circulation, controls the concentration of potassium, sodium, rubidium and cesium in mother liquor corresponding to each working procedure, and is combined with a crystallization phase through evaporation concentration, and is characterized by specifically comprising the following steps:
1) crushing, adding materials and pulping, namely crushing lepidolite into powder, sealing and stacking, and conveying the powder or prepared slurry into a reaction kettle device to obtain pretreated lepidolite powder;
2) acidifying and leaching, namely adding pretreated lithium mica powder, concentrated sulfuric acid and water into a reaction kettle device together, stirring and mixing uniformly to obtain a lithium mica acid water mixture, heating steam under the normal pressure environment condition for 3-6 hours to obtain sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium, hydrogen fluoride and fluoride generated by an acidifying reaction, acid steam and residual acid, and cooling the sulfate solution mother liquor 1 containing lithium, potassium, sodium, rubidium and cesium to obtain an acidified leaching material; hydrogen fluoride and fluoride generated by the acidification reaction and acid steam enter a tail gas recovery treatment system for treatment; neutralizing and filter-pressing the hydrogen fluoride and fluoride generated by the acidification reaction, acid steam and residual acid to obtain filtrate and filter residue 1, returning the filtrate to the water supplementing process of the acidification leaching process, and recycling or externally selling the filter residue 1;
3) Mixing and drying, namely adding water into the acidified leaching material obtained in the step 2) to prepare acidified leaching mixed solution, adding dried silica sand into the acidified leaching mixed solution, mixing and continuously stirring to prepare solid-liquid mixed solution, fully stirring and mixing the solid-liquid mixed solution, and then placing the solid-liquid mixed solution into a drying device for drying to obtain dried mixed material; the water vapor and tail gas generated during drying are treated by a tail gas recovery treatment system and sprayed and then discharged after reaching the standard;
4) acidizing and roasting, namely placing the dried and mixed material obtained in the step 3) into a roasting kiln for roasting treatment, and controlling the roasting treatment temperature to be 300-900 ℃ to obtain a roasted material; after waste gas generated by roasting enters a tail gas recovery treatment system for treatment, the waste gas is discharged after reaching the standard;
5) Water leaching reaction, namely adding water into the roasted material obtained in the step 4), stirring and mixing to obtain solid-liquid mixture, and controlling the solid-liquid mass ratio of the roasted material to the water to be 1: 1.1-1.3, carrying out water leaching treatment to obtain a solid-liquid mixed water solution, filtering and separating the solid-liquid mixed water solution after the water leaching treatment is finished to obtain a mother solution 2 and a filter residue 2, washing the filter residue 2 and drying to obtain dry silica sand;
6) primary cooling crystallization, namely placing the mother liquor 1 and the mother liquor 2 in a cooling crystallization device, and adopting circulating frozen brine for cooling treatment to obtain primary cooling crystallization under the condition of continuous stirring to obtain a mixed solution of precipitated aluminum rubidium alum and aluminum cesium alum; filtering and separating the mixed solution of aluminum, rubidium, alum and aluminum, cesium and alum to obtain a mother solution 3, a rubidium, cesium and potassium mixture of rubidium, cesium and alum and potassium, sodium and alum;
7) performing secondary cooling crystallization to prepare potassium sodium alum, adding a secondary catalytic crystallization agent into the mother liquor 3 obtained in the step 6), performing cooling secondary cooling crystallization treatment to obtain a mixed solution of aluminum sodium alum and aluminum potassium alum, and filtering and separating the mixed solution of aluminum sodium alum and aluminum potassium alum to obtain a mother liquor 4 and potassium sodium alum;
8) adding alkali to neutralize and separate gypsum solid residue, adding lime milk into the mother liquor 4 obtained in the step 7), then adding hydrogen peroxide solution to obtain a mother liquor mixed solution, generating a large amount of precipitates by controlling the pH value of the mother liquor mixed solution, and performing filter pressing and separation to obtain gypsum solid residue and a mother liquor 5;
9) Adding an impurity removal catalyst to remove impurities, adding the impurity removal catalyst into the mother liquor 5 obtained in the step 8) to remove impurities, filtering and separating to obtain solid gypsum residues and a mother liquor 6; returning the gypsum solid slag to the step 2), wherein the neutralization process is a neutralization addition raw material;
10) Evaporating and concentrating, namely putting the mother liquor 6 into an MVR high-efficiency evaporator, performing high-temperature evaporating and concentrating treatment to obtain an evaporated and concentrated solution, controlling the concentration of Li ions in the evaporated and concentrated solution to be 14-33g/L to obtain a concentrated liquor 7, and performing lithium precipitation and agitation washing on the concentrated liquor 7; recovering the condensed water generated by the high-temperature evaporation and concentration treatment into the washing water for preparing the sodium carbonate and the lithium carbonate;
11) Separating to prepare crude lithium carbonate, adding carbonate solution into the concentrated solution mother liquor 7, carrying out lithium precipitation reaction, obtaining crude lithium carbonate and mother liquor 8 after lithium precipitation, and washing the crude lithium carbonate by using heated water, wherein the mother liquor 8 after lithium precipitation is evaporated and concentrated by an evaporator until the concentration of Li 2 O in the solution is 15-30g/L, carrying out centrifugal filtration separation to obtain solid and centrifugal separation solution, drying the solid to obtain anhydrous sodium sulfate solid, and carrying out secondary lithium precipitation on the centrifugal separation solution to obtain industrial-grade lithium carbonate which is crude lithium carbonate;
12) Purifying the crude lithium carbonate to prepare battery-grade lithium carbonate, adding water into the crude lithium carbonate, fully stirring and mixing to prepare a crude lithium carbonate mixed aqueous solution, introducing CO 2 gas into the crude lithium carbonate mixed aqueous solution for dissolving, after the crude lithium carbonate is fully dissolved, decomposing under the heating condition, removing impurities, filtering and separating, drying filter residues by a dryer to obtain the battery-grade lithium carbonate, and recovering filtrate;
13) Preparing rubidium-cesium salt, namely performing back extraction on the rubidium-cesium-alum prepared in the step 6) and a rubidium-cesium-potassium mixture of potassium-sodium alum by using corresponding acid, and preparing a high-purity cesium salt product and a corresponding raffinate; and performing acid stripping by using the raffinate as a raw material to prepare a high-purity rubidium salt product.
2. The method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein the acidification leaching in the step 2) is performed by controlling the mass ratio of pretreated lepidolite powder to concentrated sulfuric acid to water to be 1: 0.8-1.05: 0.8-1.1; controlling the steam heating reaction temperature to be 80-150 ℃; the temperature reduction treatment is to control the temperature of the temperature reduction treatment to be 80-100 ℃; the neutralization is to add lime milk or lime milk made of gypsum solid residue into the residual acid for neutralization treatment, and the neutralization treatment is controlled until the pH value is 6-9.
3. the method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein the step 3) of stirring and drying is to control the solid-liquid ratio of the solid-liquid mixed liquid to be 0.3: 1-0.5: 1, controlling the drying to be drying by adopting a rotary drying kiln device, controlling the drying time to be 0.4-0.6h and controlling the drying temperature to be 100-150 ℃; and controlling the water vapor generated during drying and the tail gas generated by combustion to enter a tail gas treatment system of the rotary drying kiln, firstly spraying water to prepare dilute sulfuric acid with the concentration of 30-38Wt%, returning the dilute sulfuric acid to the acid leaching process for use, and discharging the sprayed tail gas after the tail gas is subjected to secondary treatment by soda lime absorption to reach the standard.
4. the method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein the step 5) is characterized in that water immersion reaction is carried out, the water immersion treatment time is controlled to be 1-3h, and the water immersion treatment temperature is 70-95 ℃; and (3) returning the silica sand to be used as the raw material in the steps of stirring and drying in the step 3).
5. The method as claimed in claim 1, wherein the step 6) of primary cooling crystallization is carried out at a temperature of 10-65 ℃ for 3-6 hours.
6. The method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein in step 7), secondary cooling crystallization is carried out, wherein the temperature of the secondary cooling crystallization is controlled to be-15-25 ℃, and the time is 3-6 hours; the secondary catalytic crystallization agent is a mixed solution of a plurality of or all component solutions of aminobutyric acid, hydrochloric acid, liquid ammonia, calcium chloride, magnesium chloride, sodium phosphate and sodium nitrate.
7. the method as claimed in claim 1, wherein the step 8) of adding alkali to neutralize and separate gypsum solid residue is to add 30-35wt% of lime milk and then 20-30wt% of hydrogen peroxide solution into mother liquor 4 at-15-25 ℃.
8. the method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein in the step 9), an impurity removing agent is added for removing impurities, and the impurity removing agent is a mixed solution of sulfuric acid, calcium chloride, magnesium chloride, sodium chloride and a sodium phosphate solution; the gypsum solid residue obtained by separation is calcium oxide or calcium hydroxide.
9. The method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite according to claim 1, wherein step 11) is to separate crude lithium carbonate, add sodium carbonate or potassium carbonate solution to the concentrated solution mother liquor 7, and control the reaction temperature of lithium precipitation to be 80-95 ℃; the time is 40-100 minutes.
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| CN115321562B (en) * | 2022-07-21 | 2023-10-17 | 四川顺应锂材料科技有限公司 | Method for producing lithium carbonate by lithium ore nitric acid leaching solution membrane method |
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| CN117303415B (en) * | 2023-11-30 | 2024-03-12 | 常州中源工程技术有限公司 | Technology for preparing lithium carbonate from water leaching solution after lepidolite roasting |
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