CN111943237B - Method for preparing battery grade lithium carbonate by using lithium sulfate coarse ore - Google Patents
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Abstract
The invention discloses a method for preparing battery grade lithium carbonate by using lithium sulfate coarse ores, which comprises the following steps: 1) Two-stage sizing and washing; 2) Preparing crude lithium carbonate; 3) Further sizing and carbonizing; 4) And (3) preparing battery-grade lithium carbonate. In the invention, the primary slurry washing adopts lithium chloride mother liquor and sodium sulfate solution for slurry washing, thereby reducing the loss of lithium sulfate and improving the recovery rate; the secondary slurry washing adopts a recycling solution L4 containing lithium carbonate as a slurry washing liquid, and the lithium in the recycling solution is recovered while soluble calcium and magnesium ions are dissolved; the filtrate L5 of the solid-liquid separation of the secondary slurry washing contains lithium, returns to the primary slurry washing liquid supplementing, and reduces the loss of the primary slurry washing lithium while dissolving soluble impurity ions; in the invention, the secondary lithium sulfate concentrate is dissolved by adopting the mirabilite preparation mother liquor L15, and NaCl mixed salt is separated out in the dissolving process and then lithium is precipitated; in the invention, the crude lithium carbonate is pulped by adopting the recycling solution containing lithium carbonate, so that the yield of lithium can be improved while the system discharge is reduced.
Description
Technical Field
The invention belongs to the technical field of lithium carbonate production and preparation, and particularly relates to a method for preparing battery grade lithium carbonate by using lithium sulfate coarse ores.
Background
Lithium, which is called as the 'new and expensive energy' in the 21 st century, is the lightest and most active metal element in nature, and is a new energy raw material. In nature, lithium resources are mainly present in granite pegmatite type mineral deposits, salt lake brine, seawater and geothermal water.
The most difficult development of salt lake resources in the Tibetan area is that chemical processing plants cannot be built in the lake area and the chemical processing plants are far away from the places with industrial processing capability, so that high-grade minerals can only be obtained in the lake area and then transported out for processing, and the core is to obtain serial salt pan minerals by building a salt pan by utilizing local natural environment.
The method for separating beneficial elements from sulfate type salt lake brine by natural energy enrichment can be used for obtaining lithium sulfate coarse ore with other components of NaCl and MgSO 4 ·7H 2 O and carnallite (KCl MgCl) 2 ·6H 2 O) and the like, and a small amount of sand. Because the grade of the lithium sulfate coarse ore is lower, the economic added value of the lithium sulfate coarse ore is improvedThe content of valuable lithium element is required to be increased.
At present, there are many studies on the extraction of lithium carbonate from salt lakes, for example, in patent No. 201711113491.0, "a method for preparing battery grade lithium carbonate from salt lake lithium ores," although the process is simple and battery grade lithium carbonate is obtained, lithium loss is relatively large during impurity removal, and the discharge amount thereof is large, so that the resource recovery is not thorough. In another example, in patent 201610212616.4, "a method for preparing lithium carbonate from plateau carbonate brine", a series of impurity removal processes are designed mainly by utilizing the difference of local climates, but the processes have great seasonal dependence, only primary impurity removal is performed, and the purity of the finally obtained lithium carbonate is not high. Aiming at the defects of the prior art, it is necessary to research a more reasonable process for preparing battery grade lithium carbonate by adopting lithium sulfate coarse ores.
Disclosure of Invention
The invention aims to provide a method for preparing battery grade lithium carbonate by using lithium sulfate coarse ore, which has the advantages of small lithium loss, thorough impurity removal and small external discharge.
The method for preparing battery grade lithium carbonate by adopting lithium sulfate coarse ore comprises the following steps:
1) Two-stage sizing: crushing and screening lithium sulfate coarse ores, performing primary pulp washing at a specific temperature by adopting primary pulp washing liquid, and performing solid-liquid separation after the pulp washing is finished to obtain primary lithium sulfate concentrate S1 and primary pulp washing filtrate L3; carrying out secondary slurry washing on the primary lithium sulfate concentrate S1 and the recirculating solution L4 at a specific temperature, and carrying out solid-liquid separation on the secondary slurry washing material to obtain a secondary lithium sulfate concentrate S2 and a secondary slurry washing filtrate L5; the secondary slurry wash filtrate L5 may be returned to the primary slurry wash process as part of the slurry wash;
2) Preparation of crude lithium carbonate: dissolving the secondary lithium sulfate concentrate S2 prepared in the step 1) in mirabilite preparation mother liquor L15 or sodium sulfate solution L2 at a specific temperature, before generating the solution L15, separating out NaCl-containing mixed salt by using the sodium sulfate solution L2 in the dissolving process, and then carrying out solid-liquid separation to obtain a NaCl mixed salt filter cake S3 and filtrate; performing precise filtration on the filtrate to obtain a solution L8; removing boron from the solution L8 through ion exchange to obtain a solution L9; adding the solution L9 into a lithium precipitation reactor, adding soda solution L10 for reaction, separating out lithium carbonate crystals, and carrying out solid-liquid separation on the reaction solution to obtain lithium precipitation mother solution L11 and crude lithium carbonate S4;
3) Further sizing and carbonization: the crude lithium carbonate S4 is further pulped by a recycle solution L4, and after the pulping is finished, a solution L12 and wet lithium carbonate S6 are obtained through solid-liquid separation; adding wet lithium carbonate S6 into a lithium carbonate slurrying tank, adding deionized water, slurrying at a specific temperature, pumping the slurried liquid into a carbonization reaction kettle after slurrying is finished, and then introducing CO 2 The gas and the recycled solution L4 are subjected to carbonization reaction at a specific temperature, and after the reaction is finished, the reaction solution is subjected to precise filtration to obtain a solution L13;
4) Preparation of battery grade lithium carbonate: removing calcium and magnesium from the solution L13 in the step 3) by an ion exchange method to obtain a solution L14; adding the solution L14 into a decarburization reaction kettle for decarburization reaction, and then carrying out solid-liquid separation to obtain a recycled solution L4 and wet lithium carbonate S7; drying and dehydrating wet lithium carbonate S7 to obtain lithium carbonate S8, and crushing the lithium carbonate S8 to a qualified particle size to obtain battery grade lithium carbonate S9;
wherein: the primary pulp washing liquid in the step 1) is a mixed liquid consisting of lithium chloride mother liquid L1 and sodium sulfate solution L2 or a mixed liquid consisting of lithium chloride mother liquid L1, sodium sulfate solution L2 and secondary pulp washing filtrate L5.
In the step 1), the slurry washing is performed in a slurry washing reactor, the set temperature is 60-70 ℃, the concentration of the lithium chloride mother liquor L1 is 200-500 g/L, and Na in the sodium sulfate solution L2 2 SO 4 When the concentration is 200-450 g/L and the slurry washing liquid is the combination of lithium chloride mother liquid L1 and sodium sulfate solution L2, the mixing volume ratio of the two is 0.9:1-1.2:1; when the slurry washing liquid consists of lithium chloride mother liquid L1, sodium sulfate solution L2 and secondary slurry washing filtrate L5, the volume ratio of the mixed liquid of L1 and L2 to L5 is 2:1-4:1; the solid-liquid ratio in the primary sizing process is 1:1-1.5:1; the obtained primary lithium sulfate concentrate S1 has a moisture content of 10-20%, wherein Li is 2 SO 4 The content is 20-40%; mgSO enriched in the primary slurry filtrate L3 4 And MgCl 2 Can be used for producingGypsum and bischofite, and a lithium chloride mother liquor L1 rich in lithium chloride is obtained, and a lithium chloride solution with a concentration of 200-500 g/L is adopted before the lithium chloride mother liquor L1 is not generated.
In the step 1), the set temperature is 60-70 ℃, the recycled solution L4 is the solution after decarbonization in the preparation step 4) of the battery grade lithium carbonate, and the recycled solution L4 in the step adopts the lithium carbonate solution with the concentration of 5-15 g/L before the recycled solution L4 is generated; the solid-liquid ratio in the secondary sizing process is 0.8:1-1.2:1.
In the step 2), the specific temperature is 60-70 ℃, and Na in the sodium sulfate solution L2 2 SO 4 The concentration is 200-450 g/L, and the NaCl concentration in the mother liquor L15 for preparing mirabilite is 200-350 g/L, na 2 SO 4 The concentration is 50-120 g/L, the volume ratio of the mother liquor L15 to L2 is 3:1-6:1, and the solid-liquid ratio of the secondary lithium sulfate concentrate S2 to the mixed liquor (L15 and L2) is 1:3-1:6; fine filtration can separate particles with a particle size of less than 5 μm from the solution; li in solution L8 2 SO 4 3-10% of the total content; the ion exchange boron removal is to remove boron by adopting ion exchange resin, and the concentration of the soda liquid L10 is 200-400 g/L; the volume ratio of the solution L9 to the soda solution L10 is 2:1-5:1.
In the step 3), the solid-to-liquid ratio of the crude lithium carbonate S4 to the recycled solution L4 is 1:5-1:8; the sizing temperature is 70-80 ℃; the slurry washing can adopt a one-stage slurry washing method or a multi-stage slurry washing purification method described in patent 201910152320.1; the wet lithium carbonate S6 has a moisture content of 4-20%, wherein Li 2 CO 3 80-95% of the total content; the solid-liquid ratio of wet lithium carbonate S6 to deionized water is 1:8-1:12, the set temperature is 5-15 ℃, the volume ratio of slurry to recycled solution L4 is 1:2-1:3, and before recycled solution L4 is generated, the recycled solution L4 in the step adopts lithium carbonate solution with the concentration of 5-15 g/L; the set temperature of the carbonization reaction is 15-25 ℃; fine filtration can separate particles smaller than 5 μm from the solution.
In the steps 2) and 3), na rich in the lithium precipitation mother liquor L11 and the solution L12 2 SO 4 Can be used for preparing mirabilite, so as to obtain mirabilite and mirabilite mother liquor L15, and the mirabilite can be used for preparing sodium sulfate solution L2.
The steps ofIn the step 4), the ion exchange method is a resin ion exchange method, the resin can adsorb calcium and magnesium ions, and the resin can carry out ion desorption through NaOH solution, HCl solution and deionized water so as to realize resin regeneration; the decarbonization temperature is 90-95 ℃, the moisture content of wet lithium carbonate S7 is 4.9-18%, wherein Li is 2 CO 3 The content is 82-95%; the recycled solution L4 is recycled in the system.
In the step 4), drying is carried out to remove water of wet lithium carbonate S7 to obtain lithium carbonate S8, and drying equipment can adopt hot air drying or steam drying equipment; and crushing the lithium carbonate S8 to a particle size of <5 mu m, collecting to obtain battery grade lithium carbonate S9, and storing and packaging to obtain a battery grade lithium carbonate product.
The invention has the beneficial effects that:
1. in the step 1) of the process, the primary slurry washing adopts the lithium chloride mother liquor L1 and the sodium sulfate solution L2 which are rich in lithium chloride for slurry washing, so that the loss of lithium sulfate can be reduced, and the recovery rate is improved; a secondary slurry washing of a recycle solution L4 containing lithium carbonate (which is derived from the decarbonized solution) as a slurry washing liquid, and recovery of lithium from the recycle solution while removing soluble calcium and magnesium ions; the filtrate L5 of the solid-liquid separation of the secondary slurry washing contains lithium, returns to the primary slurry washing liquid filling, and reduces the loss of the primary slurry washing lithium while dissolving soluble impurity ions.
2. In the step 2) of the process, the mirabilite preparing mother liquor L15 or sodium sulfate solution L2 is adopted to dissolve the secondary lithium sulfate concentrate S2, and the solution and Na contained in the S2 + 、K + 、Cl - 、SO 4 2- Will generate ion effect, naCl, K 2 SO 4 And the like, due to supersaturation, precipitation and crystallization, the impurity generation amount of the subsequent lithium extraction and impurity removal process and the influence on the purity of the product lithium carbonate are reduced, and meanwhile, lithium in the solution L15 is recovered; after sizing and salt precipitation, naCl, K 2 SO 4 、Na 2 B 4 O 7 The method has the advantages that a large amount of boron is removed, the boron removal efficiency is further higher by adopting the ion exchange efficiency, and the influence of impurity ions on the ion exchange is smaller; the ion exchange is adopted to remove boron, and the resin can be regenerated by NaOH solution and HCl solution, so that the cost consumption is low.
3. In step 2) of the invention, most of lithium is precipitated in the form of lithium carbonate by controlling the pH value, and the lithium precipitation mother liquor L11 is rich in a large amount of Na 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The solution L12 produced in step 3) also contains Na 2 SO 4 Therefore, the lithium precipitation mother liquor L11 and the solution L12 can be used for preparing mirabilite to obtain mirabilite and mirabilite mother liquor L15, the mirabilite can be used for preparing sodium sulfate solution L2, the material consumption and the running cost are effectively reduced, and the redundant mirabilite can be sent for sale;
4. in step 3) of the process, the crude lithium carbonate S4 adopts a recycling solution L4 containing lithium carbonate as a slurry washing liquid, wherein the recycling solution L4 can be a lithium precipitation mother solution of battery grade lithium carbonate or a newly prepared lithium carbonate solution; the purity of the product can be improved by adopting the multistage countercurrent slurry washing purification method of 201910152320.1 in the slurry washing operation, and the temperature is controlled between 70 and 80 ℃ to reduce the dissolution and loss of lithium carbonate; the solution L12 after washing the lithium carbonate slurry contains lithium carbonate, and can be used as slurry washing liquid of other crude lithium carbonate or returned to a system to improve the lithium yield. Furthermore, the deionized water is adopted to dissolve the wet lithium carbonate S6, so that the introduction amount of impurities can be reduced, the recirculating solution L4 can be introduced in the carbonization process according to the need, L4 is the solution after decarburization in the preparation step 4) of the battery-grade lithium carbonate, the system discharge is reduced, and the yield of lithium can be improved;
5. in the step 4), a small amount of calcium and magnesium ions brought by wet lithium carbonate S6 crystals are removed through ion exchange, and the resin can be regenerated by NaOH solution and HCl solution, so that the cost and the operation consumption are low; most of lithium is precipitated by lithium carbonate after decarbonization, and decarbonized mother liquor after solid-liquid separation is used as a recirculating solution L4 and returns to a system for supplementing liquid to form internal circulation.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments, but not all embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The invention will be further described with reference to the drawings and specific examples.
The solid-to-liquid ratio unit in the examples is g/mL.
Example 1
In this example, crude lithium sulfate ore produced from some sulfate type salt lake brine of Tibet was used, and the content of lithium sulfate was 17.25%.
The process flow of this embodiment is shown in fig. 1, and specifically includes the following steps:
1. primary sizing: crushing and grinding the lithium sulfate coarse ore to obtain particles with the particle size smaller than 2mm, and sending the particles into a slurry washing reactor, and performing slurry washing on the lithium sulfate coarse ore by adopting slurry washing liquid at 65 ℃; before the secondary slurry washing filtrate L5 is generated, the slurry washing liquid adopts lithium chloride mother liquor L1 (the concentration is 350 g/L) and sodium sulfate solution L2 (the concentration is 350 g/L) with the volume ratio of 1:1; when the secondary slurry washing filtrate L5 is generated, the slurry washing liquid is a combination of lithium chloride mother liquid L1, sodium sulfate solution L2 and secondary slurry washing filtrate L5, the volume ratio of the lithium chloride mother liquid L1 to the sodium sulfate solution L2 is 1:1, and the volume ratio of the mixed liquid of L1 and L2 to the L5 is 2.5:1; the solid-liquid ratio of the lithium sulfate coarse ore to the slurry is 1.2:1; after the slurry washing is finished, solid-liquid separation is carried out, the separated solid primary lithium sulfate concentrate S1 enters secondary slurry washing, and the separated slurry washing filtrate L3 is rich in MgSO (MgSO) 4 And MgCl 2 Can be used for producing gypsum and bischofite, and obtaining lithium chloride mother liquor L1 rich in lithium chloride.
After the whole process is stable, the moisture content of the primary lithium sulfate concentrate S1 obtained in the step is 15.25%, wherein Li is measured 2 SO 4 The content is 35.55%; mgSO in filtrate L3 4 9.55％、MgCl 2 14.62％、LiCl 7.35％。
2. Secondary sizing: the primary lithium sulfate concentrate S1 is subjected to secondary slurry washing at 65 ℃ by adopting a recycling solution L4, and before the solution L4 is generated, the recycling solution L4 adopts a lithium carbonate solution with the concentration of 10 g/L; during slurry washing, the solid-to-liquid ratio of the primary lithium sulfate concentrate S1 to the recycled solution L4 is 1.2:1; after the sizing is finished, solid-liquid separation is carried out, the separated solid secondary lithium sulfate concentrate S2 enters a salt dissolving and resolving step, and the separated filtrate secondary sizing filtrate L5 returns to the step 1) to be used as a part of sizing liquid.
After the whole process is stable, li in the secondary lithium sulfate concentrate S2 is measured 2 SO 4 29.35％，NaCl26.25％，K 2 SO 4 6.33％，KCl 0.08％，MgCl 2 0.83％，LiCl 0.42％。
3. Preparation of crude lithium carbonate: the secondary lithium sulfate concentrate S2 is dissolved in the glauber' S salt preparation mother liquor L15 (NaCl concentration 260g/L, na) at 65 DEG C 2 SO 4 Concentration 90g/L, KCl concentration 65g/L, li 2 CO 3 Concentration 10.5 g/L) and sodium sulfate solution L2 (Na 2 SO 4 The concentration of 420 g/L), the volume ratio of the mother solution L15 to L2 is 5:1, the solid-liquid ratio of the lithium concentrate S2 to the mixed solution is controlled to be 1:5, salt precipitation occurs in the dissolving process, and then solid-liquid separation is carried out to obtain a NaCl mixed salt filter cake S3 and filtrate; performing precise filtration on the filtrate (particles smaller than 5um in the filtered solution) to obtain a solution L8; removing boron from the solution L8 through ion exchange to obtain a solution L9; adding the solution L9 into a lithium precipitation reactor, then adding soda solution L10 for reaction (the concentration of the soda solution L10 is 300g/L, the volume ratio of the L9 to the L10 is 4:1), precipitating lithium carbonate crystals, and carrying out solid-liquid separation on the reaction solution to obtain a lithium precipitation mother solution L11 and crude lithium carbonate S4.
In the dissolution and salt precipitation process, if 22t/h of secondary lithium sulfate concentrate S2 and 100m 3 When mixing/h (the mixed solution of mother liquor L15 and L2), calculating according to the corresponding ion product at 65 ℃, and NaCl and K in the solution 2 SO 4 The aliphate will precipitate NaCl crystal 6t/h, K due to supersaturation 2 SO 4 The crystal is 1t/h, and the mixed salt mainly containing NaCl is formed.
4. Further sizing: and (3) carrying out two-stage countercurrent slurry washing on the crude lithium carbonate S4 by using a recycle solution L4 at 75 ℃ (the solid-liquid ratio of the two-stage slurry washing is 1:8), and carrying out solid-liquid separation after the slurry washing is finished to obtain a solution L12 and wet lithium carbonate S6.
After the whole process flow is stable, the moisture content of wet lithium carbonate S6 is 10 percent, wherein Li is as follows 2 CO 3 The content is 90 percent.
The solution L11 and the solution L12 can be combined to prepare mirabilite, so that mirabilite and mirabilite mother solution L15 are obtained, the mirabilite can be used for preparing sodium sulfate solution L2, and the cost is reduced while the discharge is reduced.
5. Carbonizing: adding wet lithium carbonate S6 into a lithium carbonate slurrying tank, adding deionized water according to a solid-to-liquid ratio of 1:9, slurrying at 10 ℃, pumping the slurried liquid into a carbonization reaction kettle after slurrying is finished, and then introducing CO 2 And (3) carrying out carbonization reaction on the gas and the recycled solution L4 (the volume ratio of the slurrying solution to the L4 is 1:2.5), and carrying out precise filtration (filtering impurities with the particle size smaller than 5 um) on the reaction solution after the reaction is finished to obtain a solution L13.
6. Removing calcium and magnesium and decarbonizing: removing calcium and magnesium from the solution L13 by an ion resin exchange method to obtain a solution L14; adding the solution L14 into a decarburization reaction kettle, carrying out decarburization reaction at 95 ℃, and carrying out solid-liquid separation after the reaction is finished to obtain a recycled solution L4 and wet lithium carbonate S7.
After the whole process is stable, the moisture content of the wet lithium carbonate S7 is 9 percent, wherein Li is as follows 2 CO 3 The content is 91 percent.
7. Drying and crushing: air-drying, drying and dehydrating the wet lithium carbonate S7 to obtain lithium carbonate S8, and crushing the lithium carbonate S8 to below 5um to obtain battery-grade lithium carbonate S9;
the purity of lithium carbonate S9 was 99.76%.
Supplementary explanation: in this example, when the recycled solution L4 was not produced or the recycled solution L4 was insufficient, the recycled solution 4 was a lithium carbonate solution having a concentration of 10 g/L.
TABLE 1 composition of lithium sulfate coarse ore and battery grade lithium carbonate
Claims (8)
1. A method for preparing battery grade lithium carbonate by using lithium sulfate coarse ore comprises the following steps:
1) Two-stage sizing: crushing and screening lithium sulfate coarse ores, performing primary pulp washing at a specific temperature by adopting primary pulp washing liquid, and performing solid-liquid separation after the pulp washing is finished to obtain primary lithium sulfate concentrate S1 and primary pulp washing filtrate L3; carrying out secondary slurry washing on the primary lithium sulfate concentrate S1 and the recirculating solution L4 at a specific temperature, and carrying out solid-liquid separation on the secondary slurry washing material to obtain a secondary lithium sulfate concentrate S2 and a secondary slurry washing filtrate L5; the secondary slurry wash filtrate L5 may be returned to the primary slurry wash process as part of the slurry wash;
2) Preparation of crude lithium carbonate: dissolving the secondary lithium sulfate concentrate S2 prepared in the step 1) in a mirabilite preparation mother liquor L15 or a sodium sulfate solution L2 at a specific temperature, before generating the mirabilite preparation mother liquor L15, separating out NaCl-containing mixed salt in the dissolving process by using the sodium sulfate solution L2, and then carrying out solid-liquid separation to obtain a NaCl mixed salt filter cake S3 and filtrate; performing precise filtration on the filtrate to obtain a solution L8; removing boron from the solution L8 through ion exchange to obtain a solution L9; adding the solution L9 into a lithium precipitation reactor, adding soda solution L10 for reaction, separating out lithium carbonate crystals, and carrying out solid-liquid separation on the reaction solution to obtain lithium precipitation mother solution L11 and crude lithium carbonate S4;
3) Further sizing and carbonization: the crude lithium carbonate S4 is further pulped by a recycle solution L4, and after the pulping is finished, a solution L12 and wet lithium carbonate S6 are obtained through solid-liquid separation; adding wet lithium carbonate S6 into a lithium carbonate slurrying tank, adding deionized water, slurrying at a specific temperature, pumping the slurried liquid into a carbonization reaction kettle after slurrying is finished, and then introducing CO 2 The gas and the recycled solution L4 are subjected to carbonization reaction at a specific temperature, and after the reaction is finished, the reaction solution is subjected to precise filtration to obtain a solution L13;
4) Preparation of battery grade lithium carbonate: removing calcium and magnesium from the solution L13 in the step 3) by an ion exchange method to obtain a solution L14; adding the solution L14 into a decarburization reaction kettle for decarburization reaction, and then carrying out solid-liquid separation to obtain a recycled solution L4 and wet lithium carbonate S7; drying and dehydrating wet lithium carbonate S7 to obtain lithium carbonate S8, and crushing the lithium carbonate S8 to a qualified particle size to obtain battery grade lithium carbonate S9;
wherein: the primary pulp washing liquid in the step 1) is mixed liquid composed of lithium chloride mother liquid L1 and sodium sulfate solution L2 or mixed liquid composed of lithium chloride mother liquid L1, sodium sulfate solution L2 and secondary pulp washing filtrate L5;
in the step 1), the slurry washing is performed in a slurry washing reactor, the primary slurry washing set temperature is 60-70 ℃, the concentration of lithium chloride mother liquor L1 is 200-500 g/L, and Na in sodium sulfate solution L2 2 SO 4 When the concentration is 200-450 g/L and the slurry washing liquid is the combination of lithium chloride mother liquid L1 and sodium sulfate solution L2, the mixing volume ratio of the two is 0.9:1-1.2:1; when the slurry washing liquid consists of lithium chloride mother liquid L1, sodium sulfate solution L2 and secondary slurry washing filtrate L5, the volume ratio of the mixed liquid of L1 and L2 to L5 is 2:1-4:1; the solid-liquid ratio in the primary sizing process is 1:1-1.5:1; the moisture content of the obtained primary lithium sulfate concentrate S1 is 10-20%, wherein Li 2 SO 4 The content is 20-40%; mgSO enriched in the primary slurry filtrate L3 4 And MgCl 2 Can be used for producing gypsum and bischofite, and can obtain lithium chloride mother liquor L1 rich in lithium chloride;
in the step 1), the set temperature of the secondary slurry washing is 60-70 ℃, the recycled solution L4 is the solution after decarbonization in the preparation step 4) of the battery-grade lithium carbonate, and before the recycled solution L4 is generated, the recycled solution L4 in the step adopts a lithium carbonate solution with the concentration of 5-15 g/L; the solid-liquid ratio in the secondary sizing and washing process is 0.8:1-1.2:1;
in the step 2), the specific temperature is 60-70 ℃;
in the step 3), the specific temperature of slurrying is 5-15 ℃, and the set temperature of carbonization reaction is 15-25 ℃.
2. The method for preparing battery grade lithium carbonate from coarse lithium sulfate ore according to claim 1, wherein in the step 2), na in the sodium sulfate solution L2 2 SO 4 The concentration is 200-450 g/L, and the NaCl concentration in the glauber's salt preparation mother solution L15 is 200-350 g/L, na 2 SO 4 The concentration is 50-120 g/L, the volume ratio of the mother liquor L15 to the mother liquor L2 is 3:1-6:1, and the solid-liquid ratio of the secondary lithium sulfate concentrate S2 to the mixed liquor of the L15 and the L2 is 1:3-1:6; fine filtration can separate particles smaller than 5 μm from the solution.
3. According to claimThe method for preparing battery grade lithium carbonate from coarse lithium sulfate ore as claimed in claim 1, wherein Li in solution L8 2 SO 4 3-10% of the content; the ion exchange boron removal is to remove boron by adopting ion exchange resin, and the concentration of the soda liquid L10 is 200-400 g/L; the volume ratio of the solution L9 to the soda solution L10 is 2:1-5:1.
4. The method for preparing battery grade lithium carbonate from coarse lithium sulfate ore according to claim 1, wherein in the step 3), the solid-to-liquid ratio of the coarse lithium carbonate S4 to the recycled solution L4 is 1:5-1:8; the sizing temperature is 70-80 ℃; the slurry washing can adopt a primary slurry washing or a multi-stage slurry washing purification method; the wet lithium carbonate S6 has a moisture content of 4-20%, wherein Li 2 CO 3 80-95% of the total content.
5. The method for preparing battery grade lithium carbonate from coarse lithium sulfate ore according to claim 1, wherein in the step 3), the solid-to-liquid ratio of wet lithium carbonate S6 to deionized water is 1:8-1:12, the volume ratio of slurry to recycled solution L4 is 1:2-1:3, and before the recycled solution L4 is generated, the recycled solution L4 in the step adopts a lithium carbonate solution with a concentration of 5-15 g/L; fine filtration can separate particles smaller than 5 μm from the solution.
6. The method for preparing battery grade lithium carbonate from coarse lithium sulfate ore according to claim 1, wherein in the steps 2) and 3), the lithium precipitation mother liquor L11 and the solution L12 are rich in Na 2 SO 4 Can be used for preparing mirabilite, so as to obtain mirabilite and mirabilite mother liquor L15, and the mirabilite can be used for preparing sodium sulfate solution L2.
7. The method for preparing battery grade lithium carbonate from lithium sulfate coarse ore according to claim 1, wherein in the step 4), the ion exchange method is a resin ion exchange method, the resin can adsorb calcium and magnesium ions, and the resin can be subjected to ion desorption through NaOH solution, HCl solution and deionized water to realize resin regeneration; the decarbonization temperature is 90-95 ℃, and the moisture content of wet lithium carbonate S7 is 4.9-18%, whereinLi 2 CO 3 The content is 82-95%; the recycled solution L4 is recycled in the system.
8. The method for preparing battery grade lithium carbonate from coarse lithium sulfate ore according to claim 1, wherein in the step 4), the wet lithium carbonate S7 is dried and water is removed to obtain lithium carbonate S8, and the drying equipment can be hot air drying or steam drying equipment; and after the lithium carbonate S8 is crushed to the particle size of <5 mu m, collecting to obtain battery-grade lithium carbonate S9, and storing and packaging to obtain a battery-grade lithium carbonate product.
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