CN110217806B - Method for preparing large-particle lithium carbonate from salt lake lithium-rich brine - Google Patents

Method for preparing large-particle lithium carbonate from salt lake lithium-rich brine Download PDF

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CN110217806B
CN110217806B CN201910607578.6A CN201910607578A CN110217806B CN 110217806 B CN110217806 B CN 110217806B CN 201910607578 A CN201910607578 A CN 201910607578A CN 110217806 B CN110217806 B CN 110217806B
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lithium
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salt lake
rich brine
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CN110217806A (en
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马艳芳
张志宏
李成宝
刘鑫
李志伟
苏彤
张永明
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Qinghai Institute of Salt Lakes Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Abstract

The invention discloses a method for preparing large-particle lithium carbonate from salt lake lithium-rich brine, which comprises the following steps: step 1, heating salt lake lithium-rich brine to 70-85 ℃, maintaining the temperature after heating is completed, and adding a surfactant into the salt lake lithium-rich brine; step 2, maintaining the temperature in the step 1, adding a carbonate solution into the pretreated saline lake lithium-rich brine, and reacting for 1-3 hours to obtain reaction product slurry; and 3, standing the reaction product slurry for 10-20 hours, then carrying out solid-liquid separation, and washing and drying the obtained solid particles to obtain large-particle lithium carbonate. The particle size of lithium carbonate is increased in the precipitation process by adding a certain amount of surfactant into the reaction system, the obtained lithium carbonate particles d (0.9): 300-.

Description

Method for preparing large-particle lithium carbonate from salt lake lithium-rich brine
Technical Field
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a method for preparing large-particle lithium carbonate from salt lake lithium-rich brine.
Background
The process route of extracting lithium from salt lake brine can be summarized into the processes of preparing lithium-rich brine and purifying (deeply removing lithium)Impurity), lithium carbonate precipitation 3 processes; the purification process is divided into two processes, namely magnesium-lithium separation and deep impurity removal of the brine with high magnesium-lithium ratio, wherein the magnesium-lithium separation generally adopts an ion membrane electrodialysis method. (deep impurity removal) is to carry out Li on the lithium-rich brine in the salt pan+The separation process from impurity elements directly affects Li2CO3Quality and yield of the product. The lithium carbonate precipitation process is to add alkali into the purified lithium-rich solution to precipitate Li2CO3The process of producing the product is to determine Li2CO3The key of the product.
In the prior art, salt lake brine is used as a raw material, a solution rich in lithium ions is obtained after preliminary purification and impurity removal, a sodium carbonate solution is added into the solution to precipitate a primary lithium carbonate product, and then the primary lithium carbonate is used as the raw material to further prepare a high-purity lithium carbonate product. The purity of the primary lithium carbonate product prepared by the prior process technology is less than or equal to 95 percent.
The prior art has the problems of long process flow of post-refining and carbonization, high equipment requirement, high energy consumption and the like caused by low purity and yield of the primary lithium carbonate product. The lithium carbonate produced by the prior art has the particle size d (0.9) of 10-39 microns, and has low yield and purity due to small lithium carbonate particles, so that the lithium carbonate product has poor fluidity in actual production, serious wall sticking phenomenon and high equipment loss rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing large-particle lithium carbonate from salt lake lithium-rich brine.
The invention is realized by the following technical scheme:
a method for preparing large-particle lithium carbonate from salt lake lithium-rich brine comprises the following steps:
step 1, heating salt lake lithium-rich brine to 70-85 ℃, maintaining the temperature after heating, and adding a surfactant into the salt lake lithium-rich brine, wherein the addition amount of the surfactant is 2% -10% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt, sodium dodecyl sulfate and sodium hexametaphosphate, wherein the mass content of the polypropylene ammonium salt in the surfactant is 0.5-2%, the mass content of the sodium dodecyl sulfate is 0.5-1%, and the mass content of the sodium hexametaphosphate is 0.1-0.5%;
step 2, maintaining the temperature in the step 1, adding a carbonate solution into the pretreated salt lake lithium-rich brine, wherein the addition amount of the carbonate solution is 30-45% of the mass of the salt lake lithium-rich brine, and reacting for 1-3 hours to obtain a reaction product slurry, wherein the mass concentration of the carbonate solution is 25-30%;
and 3, standing the reaction product slurry for 10-20 hours, then carrying out solid-liquid separation, and washing and drying the obtained solid particles to obtain large-particle lithium carbonate.
In the technical scheme, the molecular weight of the polypropylene ammonium salt is 3-10 ten thousand daltons.
In the above technical scheme, the carbonate solution is a sodium carbonate solution or an ammonium carbonate solution.
In the technical scheme, the salt lake lithium-rich brine is stirred in the processes of the step 1 and the step 2.
In the technical scheme, the content of lithium ions in the salt lake lithium-rich brine is 2-3 wt%, the content of potassium ions is 0.1-0.4 wt%, the content of magnesium ions is 0.08-0.1 wt%, the content of sodium ions is 0.2-1 wt%, and the content of sulfate radicals is 0.02-0.1 wt%.
In the technical scheme, the mass of the surfactant added per minute in the step 1 is 0.2-0.5% of the mass of the salt lake lithium-rich brine.
In the technical scheme, the mass of the sodium carbonate solution added per minute in the step 2 is 0.5-1.5% of the mass of the salt lake lithium-rich brine.
In the above technical scheme, the washing process in the step 3 is two times of washing, the detergent for the first time of washing is alcohol, and the detergent for the second time of washing is deionized water.
In the technical scheme, in step 3, the reaction product slurry is kept stand for 10-20 hours, then solid-liquid separation is carried out, the obtained solid particles are subjected to first washing, alcohol is used as a detergent for the first washing, the adding amount of the alcohol is 15% -30% of the mass of the solid particles, a first washing solid is obtained after the first solid-liquid separation is carried out after the first washing, the obtained first washing solid is subjected to second washing, deionized water is used as a detergent for the second washing, the adding amount of the deionized water is the same as the mass of the detergent for the first washing, a second washing solid is obtained through the second solid-liquid separation after the second washing, and the second washing solid is dried to obtain large-particle lithium carbonate.
In the technical scheme, the particle size of the large-particle lithium carbonate is d (0.9):300-600 microns.
The invention has the advantages and beneficial effects that:
the invention aims at the relevant work of the technical process of removing impurities from salt lake brine, taking the salt lake brine as a raw material liquid for precipitating lithium carbonate, adding sodium carbonate into the salt lake brine and precipitating the lithium carbonate. The particle size of the lithium carbonate is increased in the precipitation process by adding a certain amount of surfactant into the reaction system, the obtained lithium carbonate particles d (0.9) are 300-600 microns, the impurity ions adsorbed on the surface of the lithium carbonate product are reduced, the purity and the yield of the primary product are improved, and the purity of the primary product is more than or equal to 95 percent.
Drawings
Fig. 1 is a particle size distribution diagram of lithium carbonate prepared in comparative example 1 of the present invention.
Fig. 2 is a particle size distribution diagram of lithium carbonate prepared in comparative example 2 of the present invention.
Fig. 3 is a particle size distribution diagram of lithium carbonate prepared in comparative example 3 of the present invention.
Fig. 4 is a particle size distribution diagram of lithium carbonate prepared in comparative example 4 of the present invention.
Fig. 5 is a distribution diagram of the particle size of large particle lithium carbonate prepared in example 1 of the present invention.
Fig. 6 is an SEM image of lithium carbonate prepared in comparative example 1 and large particle lithium carbonate prepared in example 1 of the present invention, wherein a: lithium carbonate prepared in comparative example 1; b: large particle lithium carbonate prepared in example 1.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Comparative example 1
The method for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content in the salt lake lithium-rich brine to be 2.17 wt%, the potassium ion content to be 0.1 wt%, the magnesium ion content to be 0.08 wt%, the sodium ion content to be 0.22 wt% and the sulfate radical content to be 0.09 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 77 ℃, maintaining stirring and adding 73g of sodium carbonate solution at the temperature after heating is finished, wherein the mass of the sodium carbonate solution added per minute is 0.7% of the mass of the salt lake lithium-rich brine, and reacting for 1.5 hours to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 28%;
and 2, standing the reaction product slurry for 17 hours, then carrying out solid-liquid separation, carrying out first washing on 31.1g of obtained solid particles, wherein 7g of deionized water is adopted for the first washing as a washing agent, carrying out first solid-liquid separation after the first washing to obtain a first washing solid, carrying out second washing on the obtained first washing solid, wherein 7g of deionized water is adopted for the second washing as a washing agent, carrying out second solid-liquid separation after the second washing to obtain 30.0g of a second washing solid, and drying the second washing solid to obtain 25g of lithium carbonate.
The obtained lithium carbonate is analyzed by a laser particle sizer Mastersize 2000, and the test conditions are as follows: the refractive index of the particles is 1.567, the absorptivity of the particles is 0.1, the light shading degree is 19.64 percent, the name of a dispersing agent is Ethanol, and the refractive index of the dispersing agent is 1.360.
The particle size of the lithium carbonate is d (0.9) 39.234 micrometers, and the lithium ion content is 13.7%; the purity was 72.1% and the yield was 87.6%.
Comparative example 2
The method for preparing large-particle lithium carbonate from salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content in the salt lake lithium-rich brine to be 2.33 wt%, the potassium ion content to be 0.2 wt%, the magnesium ion content to be 0.09 wt%, the sodium ion content to be 0.35 wt% and the sulfate radical content to be 0.09 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 80 ℃, maintaining the stirring and the temperature after heating, and adding 9g of surfactant into the salt lake lithium-rich brine, wherein the adding mass of the surfactant per minute is 0.30% of the water mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of sodium hexametaphosphate, and the mass content of the sodium hexametaphosphate in the surfactant is 0.4%;
step 2, maintaining the stirring and temperature in the step 1, adding 75g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 0.9% of the mass of the salt lake lithium-rich brine, and reacting for 2 hours to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 26%;
and 3, standing the reaction product slurry for 15 hours, then carrying out solid-liquid separation, carrying out first washing on 30g of obtained solid particles, wherein 9g of alcohol is adopted as a detergent for the first washing, a first washing solid is obtained after the first solid-liquid separation is carried out on the first washing, carrying out second washing on the obtained first washing solid, 9g of deionized water is adopted as the detergent for the second washing, carrying out second solid-liquid separation on the second washing solid to obtain 29.1g of a second washing solid, and drying the second washing solid to obtain 22.3g of lithium carbonate.
The obtained lithium carbonate is analyzed by a laser particle sizer Mastersize 2000, and the test conditions are as follows: the refractive index of the particles is 1.567, the absorptivity of the particles is 0.1, the light shading degree is 13.84%, the name of a dispersing agent is Ethanol, and the refractive index of the dispersing agent is 1.360.
The particle size of the lithium carbonate is d (0.9) 112.54 micrometers, and the lithium ion content is 16%; the purity was 84.7% and the yield was 85.1%.
Comparative example 3
The method for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content in the salt lake lithium-rich brine to be 2.78 wt%, the potassium ion content to be 0.3 wt%, the magnesium ion content to be 0.085 wt%, the sodium ion content to be 0.82 wt% and the sulfate radical content to be 0.06 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 81 ℃, maintaining the stirring and the temperature after heating, and adding 9.02g of surfactant into the salt lake lithium-rich brine, wherein the mass of the surfactant added per minute is 0.43% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt (with the molecular weight of 3-10 ten thousand daltons), and the mass content of the polypropylene ammonium salt in the surfactant is 1.2%;
step 2, maintaining the stirring and temperature in the step 1, adding 74g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 1.1% of the mass of the salt lake lithium-rich brine, and reacting for 2.5 hours to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 27%;
and 3, standing the reaction product slurry for 17 hours, then carrying out solid-liquid separation, carrying out first washing on 32.1g of obtained solid particles, wherein 10g of alcohol is adopted as a detergent for the first washing, carrying out first solid-liquid separation on the first washed solid to obtain a first washed solid, carrying out second washing on the obtained first washed solid, wherein 10g of deionized water is adopted as the detergent for the second washing, carrying out second solid-liquid separation on the second washed solid to obtain 31.1g of a second washed solid, and drying the second washed solid to obtain 24.1g of lithium carbonate.
The obtained lithium carbonate is analyzed by a laser particle sizer Mastersize 2000, and the test conditions are as follows: the refractive index of the particles is 1.567, the absorptivity of the particles is 0.1, the light shading degree is 15.99 percent, the name of a dispersant is Ethanol, and the refractive index of the dispersant is 1.360.
The particle diameter of the lithium carbonate is d (0.9) 329.19 micrometers, and the lithium ion content is 17.1%; purity 90.0%, yield 82.4%.
Comparative example 4
The method for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content in the salt lake lithium-rich brine to be 2.90 wt%, the potassium ion content to be 0.40 wt%, the magnesium ion content to be 0.10 wt%, the sodium ion content to be 0.90 wt% and the sulfate radical content to be 0.05 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 84 ℃, maintaining the stirring and the temperature after the heating is finished, and adding 8.3g of surfactant into the salt lake lithium-rich brine, wherein the mass of the surfactant added per minute is 0.47% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of sodium dodecyl sulfate, and the mass content of the sodium dodecyl sulfate in the surfactant is 0.81%;
step 2, maintaining the stirring and temperature in the step 1, adding 76g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 1.4% of the mass of the salt lake lithium-rich brine, and reacting for 2.9 hours to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 29%;
and 3, standing the reaction product slurry for 19 hours, then carrying out solid-liquid separation, carrying out first washing on 27.0g of obtained solid particles, wherein 8g of alcohol is adopted as a detergent for the first washing, a first washing solid is obtained after the first washing and the first solid-liquid separation, carrying out second washing on the obtained first washing solid, 8g of deionized water is adopted as the detergent for the second washing, 25.0g of a second washing solid is obtained through the second solid-liquid separation after the second washing, and drying the second washing solid to obtain 23.7g of lithium carbonate.
The obtained lithium carbonate is analyzed by a laser particle sizer Mastersize 2000, and the test conditions are as follows: the refractive index of the particles is 1.567, the absorptivity of the particles is 0.1, the light shading degree is 16.49 percent, the name of a dispersant is Ethanol, and the refractive index of the dispersant is 1.360.
The particle size of the lithium carbonate is d (0.9) 199.9 micrometers, and the lithium ion content is 17.0%; purity 89.5%, yield 77.2%.
Example one
The method for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content of the salt lake lithium-rich brine to be 2.52 wt%, the potassium ion content to be 0.25 wt%, the magnesium ion content to be 0.09 wt%, the sodium ion content to be 0.74 wt% and the sulfate radical content to be 0.08 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 78 ℃, maintaining the stirring and the temperature after heating, and adding 7.4g of surfactant into the salt lake lithium-rich brine, wherein the mass of the surfactant added per minute is 0.35% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt (with the molecular weight of 3-10 ten thousand daltons), sodium dodecyl sulfate and sodium hexametaphosphate, wherein the mass content of the polypropylene ammonium salt in the surfactant is 2%, the mass content of the sodium dodecyl sulfate is 0.5%, and the mass content of the sodium hexametaphosphate is 0.33%;
step 2, maintaining the stirring and temperature in the step 1, and adding 77g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 1% of the mass of the salt lake lithium-rich brine, and reacting for 2 hours to obtain a reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 28%;
and 3, standing the reaction product slurry for 15 hours, then carrying out solid-liquid separation, carrying out first washing on 30.4g of obtained solid particles, wherein 6g of alcohol is adopted as a detergent for the first washing, a first washing solid is obtained after the first washing and the first solid-liquid separation, carrying out second washing on the obtained first washing solid, 6g of deionized water is adopted as the detergent for the second washing, 30.0g of a second washing solid is obtained through the second solid-liquid separation after the second washing, and drying the second washing solid to obtain 24.0g of large-particle lithium carbonate.
The obtained large-particle lithium carbonate is analyzed by a laser particle sizer Mastersize 2000, and the test conditions are as follows: the refractive index of the particles is 1.567, the absorptivity of the particles is 0.1, the light shading degree is 14.72 percent, the name of a dispersing agent is Ethanol, and the refractive index of the dispersing agent is 1.360.
The particle size of the large-particle lithium carbonate is d (0.9) 524 microns, and the lithium ion content is 18.4%; the purity was 98.9% and the yield was 97.4%.
The method has the advantages that a trace amount of composite surfactant solution is added into a crystallization system, the flowability of the system is increased, the surface performance is high, the steric hindrance is increased, the diffusion of lithium ions and carbonate ions in the solution is facilitated, the good spreadability is realized, the wall sticking phenomenon of lithium carbonate is reduced, the flowability is enhanced, the particle size of the lithium carbonate is increased, and the adsorption of impurities on the surfaces of particles is prevented.
Comparative examples 1 to 4, which describe the results of tests in which sodium hexametaphosphate aqueous solution, polypropylene-based ammonium salt, and sodium dodecyl sulfate aqueous solution were added to a pure system, respectively, during crystallization of lithium carbonate, and example 1, which describes the results of tests in which a complex surfactant was added to a system, are shown in table 1.
TABLE 1 comparison of the effect of surfactants on lithium carbonate particle size
Figure BDA0002119169310000071
The results show that lithium carbonate prepared without surfactant addition has small particles and low purity, and agglomeration is severe in the SEM in fig. 6 a. When a single additive is added into a crystallization system, the particle size and the purity of the lithium carbonate are both improved, but the expected target is not achieved, the particle size and the purity of the lithium carbonate product are greatly improved by adding the novel composite additive, and as shown in the SEM of figure 6b, the lithium carbonate is uniformly distributed, has regular appearance and larger particles.
The process for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine has the advantages of reducing energy consumption, enhancing fluidity, prolonging the service life of the crystallizer and improving the comprehensive utilization degree of salt lake resources.
Example two
The method for preparing the large-particle lithium carbonate from the salt lake lithium-rich brine comprises the following steps of enabling the lithium ion content in the salt lake lithium-rich brine to be 2.00 wt%, the potassium ion content to be 0.1 wt%, the magnesium ion content to be 0.08 wt%, the sodium ion content to be 0.20 wt% and the sulfate radical content to be 0.02 wt%.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 70 ℃, maintaining the stirring and the temperature after heating, and adding 10g of surfactant into the salt lake lithium-rich brine, wherein the mass of the surfactant added per minute is 0.2% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt (with the molecular weight of 3-10 ten thousand daltons), sodium dodecyl sulfate and sodium hexametaphosphate, wherein the mass content of the polypropylene ammonium salt in the surfactant is 0.5%, the mass content of the sodium dodecyl sulfate is 1%, and the mass content of the sodium hexametaphosphate is 0.1%;
step 2, maintaining the stirring and temperature in the step 1, adding 80g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 0.5% of the mass of the salt lake lithium-rich brine, and reacting for 3 hours to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 25%;
and 3, standing the reaction product slurry for 10 hours, then carrying out solid-liquid separation, carrying out first washing on 28.5g of obtained solid particles, wherein 10g of alcohol is adopted as a detergent for the first washing, carrying out first solid-liquid separation on the first washing to obtain a first washing solid, carrying out second washing on the obtained first washing solid, wherein 10g of deionized water is adopted as the detergent for the second washing, carrying out second solid-liquid separation on the second washing to obtain 25.0g of a second washing solid, and drying the second washing solid to obtain 19.0g of large-particle lithium carbonate.
The particle size of the large-particle lithium carbonate is d (0.9) 600 microns, and the lithium ion content is 18.7%; the purity was 99.1% and the yield 98.7%.
EXAMPLE III
The method for preparing large-particle lithium carbonate from salt lake lithium-rich brine comprises the following steps of 3.00 wt% of lithium ions, 0.4 wt% of potassium ions, 0.1 wt% of magnesium ions, 1.00 wt% of sodium ions and 0.10 wt% of sulfate radicals.
The method comprises the following steps:
step 1, stirring and heating 180g of salt lake lithium-rich brine to 85 ℃, maintaining the stirring and the temperature after heating, and adding 10g of surfactant into the salt lake lithium-rich brine, wherein the mass of the surfactant added per minute is 0.5% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt (with the molecular weight of 3-10 ten thousand daltons), sodium dodecyl sulfate and sodium hexametaphosphate, wherein the mass content of the polypropylene ammonium salt in the surfactant is 1.21%, the mass content of the sodium dodecyl sulfate is 0.79%, and the mass content of the sodium hexametaphosphate is 0.5%;
step 2, maintaining the stirring and temperature in the step 1, adding 65g of sodium carbonate solution into the pretreated salt lake lithium-rich brine, wherein the mass of the sodium carbonate solution added per minute is 1.5% of the mass of the salt lake lithium-rich brine, and reacting for 1 hour to obtain reaction product slurry, wherein the mass concentration of the sodium carbonate solution is 30%;
and 3, standing the reaction product slurry for 20 hours, then carrying out solid-liquid separation, carrying out first washing on 32.7g of obtained solid particles, wherein 5g of alcohol is adopted as a detergent for the first washing, a first washing solid is obtained after the first solid-liquid separation is carried out on the first washing, carrying out second washing on the obtained first washing solid, 5g of deionized water is adopted as a detergent for the second washing, 31.4g of a second washing solid is obtained through the second solid-liquid separation after the second washing, and drying the second washing solid to obtain 29.2g of large-particle lithium carbonate.
The particle size of the large-particle lithium carbonate is d (0.9):300 microns, and the lithium ion content is 18.0%; the purity was 95.7% and the yield was 96.7%.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (9)

1. A method for preparing large-particle lithium carbonate from salt lake lithium-rich brine is characterized by comprising the following steps:
step 1, heating salt lake lithium-rich brine to 70-85 ℃, maintaining the temperature after heating, and adding a surfactant into the salt lake lithium-rich brine, wherein the addition amount of the surfactant is 2-10% of the mass of the salt lake lithium-rich brine, so as to obtain pretreated salt lake lithium-rich brine;
the surfactant is an aqueous solution of polypropylene ammonium salt, sodium dodecyl sulfate and sodium hexametaphosphate, wherein the mass content of the polypropylene ammonium salt in the surfactant is 0.5-2%, the mass content of the sodium dodecyl sulfate is 0.5-1%, and the mass content of the sodium hexametaphosphate is 0.1-0.5%;
step 2, maintaining the temperature in the step 1, adding a carbonate solution into the pretreated salt lake lithium-rich brine, wherein the addition amount of the carbonate solution is 30-45% of the mass of the salt lake lithium-rich brine, and reacting for 1-3 hours to obtain a reaction product slurry, wherein the mass concentration of the carbonate solution is 25-30%;
step 3, standing the reaction product slurry for 10-20 hours, then carrying out solid-liquid separation, and washing and drying the obtained solid particles to obtain large-particle lithium carbonate;
the content of lithium ions in the salt lake lithium-rich brine is 2-3 wt%, the content of potassium ions is 0.1-0.4 wt%, the content of magnesium ions is 0.08-0.1 wt%, the content of sodium ions is 0.2-1 wt%, and the content of sulfate radicals is 0.02-0.1 wt%.
2. The method of claim 1, wherein the molecular weight of the polypropylene ammonium salt is 3 to 10 ten thousand daltons.
3. The method of claim 1, wherein the carbonate solution is a sodium carbonate solution or an ammonium carbonate solution.
4. The method for preparing large-particle lithium carbonate from the salt lake lithium-rich brine according to claim 1, wherein the processes of step 1 and step 2 are performed while the salt lake lithium-rich brine is stirred.
5. The method for preparing large-particle lithium carbonate from the salt lake lithium-rich brine as claimed in claim 1, wherein the mass of the surfactant added per minute in step 1 is 0.2-0.5% of the mass of the salt lake lithium-rich brine.
6. The method for preparing large-particle lithium carbonate from the salt lake lithium-rich brine as claimed in claim 3, wherein the mass of the sodium carbonate solution added per minute in the step 2 is 0.5-1.5% of the mass of the salt lake lithium-rich brine.
7. The method of claim 1, wherein the washing process in step 3 is two times, the detergent in the first washing is alcohol, and the detergent in the second washing is deionized water.
8. The method of claim 1, wherein the method for preparing large-particle lithium carbonate from the lithium-rich brine in the salt lake, it is characterized in that in step 3, the slurry of the reaction product is kept stand for 10 to 20 hours, then solid-liquid separation is carried out, the obtained solid particles are washed for the first time, the first washing adopts alcohol as a detergent, the adding amount of the alcohol is 15-30% of the mass of the solid particles, a first washing solid is obtained after first solid-liquid separation after the first washing, the obtained first washing solid is subjected to second washing, and the second washing adopts deionized water as a washing agent, the adding mass of the deionized water is the same as that of the washing agent of the first washing, secondary washing solid is obtained through secondary solid-liquid separation after the second washing, and the secondary washing solid is dried to obtain the large-particle lithium carbonate.
9. The method for preparing large-particle lithium carbonate from the lithium-rich brine in the salt lake of claim 1, wherein the particle size of the large-particle lithium carbonate is d (0.9):300-600 μm.
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