CN114014340A - Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio - Google Patents
Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio Download PDFInfo
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- 239000012267 brine Substances 0.000 title claims abstract description 132
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 121
- 239000011575 calcium Substances 0.000 title claims abstract description 100
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 67
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 title claims abstract description 24
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 43
- 239000001110 calcium chloride Substances 0.000 claims abstract description 43
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 238000007710 freezing Methods 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 230000008014 freezing Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 46
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000013505 freshwater Substances 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- -1 K +) exist Chemical class 0.000 description 25
- 239000004615 ingredient Substances 0.000 description 14
- 230000009467 reduction Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 7
- 238000004094 preconcentration Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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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
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio, which comprises the following steps: (1) naturally evaporating the calcium chloride type salt lake lithium-containing raw brine to separate out potassium and sodium mixed salt, and then acidifying the brine to remove boron; (2) and (2) carrying out natural evaporation-calcium separation freezing operation on the brine treated in the step (1) at least 1 time, wherein the calcium separation freezing operation is to cool the brine to separate out calcium chloride crystals, and then carrying out solid-liquid separation to obtain the concentrated brine enriched with lithium. The method has the characteristics of simple process, simple and convenient operation, high calcium-lithium separation efficiency and low consumption of energy, water and chemical reagents, is particularly suitable for extracting lithium from the salt lake brine with high calcium-lithium ratio in areas with poor infrastructure and insufficient energy supply, and has practical significance for the utilization of salt lake lithium resources.
Description
Technical Field
The invention belongs to the technical field of lithium extraction in salt lakes, and particularly relates to a method for removing calcium and enriching lithium from salt lake brine with a high calcium-lithium ratio.
Background
Lithium and lithium compounds such as lithium chloride, lithium carbonate, lithium hydroxide and organic lithiated compounds are widely applied to the fields of high-energy batteries, aerospace, nuclear power generation and the like, and have important significance for the development of national economy in China. Lithium is a main positive electrode material of a high-energy battery and has an important strategic position in the development of energy storage materials and clean nuclear energy. With the rapid development of science and technology and the rising demand of energy, the challenge of energy is very large, and lithium batteries gradually become the mainstream of the battery industry.
The lithium resource of the salt lake accounts for more than 69 percent of the industrial reserves of the lithium resource in the world, and the extraction of lithium from the brine of the salt lake is the key of the energy competition strategic high land in China and is the national major strategic demand. The world source of lithium in salt lakes is mainly distributed in south america, north america and asia; salt lake areas are often sparsely populated, the infrastructure is not complete, and the energy supply is insufficient, so that serious restrictions are brought to the development and utilization of the lithium resources. The method for extracting lithium from brine mainly comprises various methods such as an evaporation crystallization method, a precipitation method, an extraction method, an adsorption method, a calcination method, a membrane separation method and the like.
Wherein, the evaporative crystallization method and the precipitation method are mainly used for extracting lithium from salt lake brine with low magnesium-lithium ratio and calcium-lithium ratio; although the extraction method, the adsorption method, the calcination method, the membrane separation method and the like can be applied to extracting lithium from salt lake brine with high magnesium-lithium ratio and high calcium-lithium ratio, the method has certain problems. If high-concentration hydrochloric acid is required to be added in the extraction method for carrying out back extraction, equipment is seriously corroded, and an organic solvent is easy to enter extracted brine, so that great pollution is caused to salt lake brine; the aluminum adsorption method in the adsorption method has good industrial application condition, but also has the problems of high investment, high water consumption and high power consumption; the manganese-based and titanium-based adsorption methods have large acid and alkali consumption, and also have the problems of high dissolving loss of the adsorbent, high energy consumption and the like; a large amount of hydrochloric acid as a byproduct of the calcining method seriously corrodes equipment, and the process needs to evaporate a large amount of water, so that the energy consumption is high; the electrodialysis method can only separate +1 and +2 valent ions, and under the condition that other +1 valent impurity ions (such as K +) exist, the separation efficiency is low, and the service cycle of the filter membrane is short. Therefore, the technology for extracting lithium from the salt lake brine with high calcium-lithium ratio, which is simple, efficient, energy-saving and environment-friendly, is especially important.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the method for removing calcium and enriching lithium from the salt lake brine with high calcium-lithium ratio has the characteristics of simple process, simple and convenient operation, high calcium-lithium separation efficiency and low energy, water and chemical reagent consumption, is particularly suitable for extracting lithium from the salt lake brine with high calcium-lithium ratio in areas with poor infrastructure and insufficient energy supply, and has practical significance for the utilization of salt lake lithium resources.
The technical purpose of the invention is realized by the following technical scheme:
a method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio comprises the following steps:
(1) naturally evaporating the calcium chloride type salt lake lithium-containing raw brine to separate out potassium and sodium mixed salt, and then acidifying the brine to remove boron;
(2) and (2) carrying out natural evaporation-calcium separation freezing operation on the brine treated in the step (1) at least 1 time, wherein the calcium separation freezing operation is to cool the brine to separate out calcium chloride crystals, and then carrying out solid-liquid separation to obtain the concentrated brine enriched with lithium.
Preferably, in the step (1), the mass ratio of Ca/Li in the lithium-containing raw brine in the calcium chloride type salt lake is more than 10.
More preferably, in the step (1), the mass ratio of Ca/Li in the calcium chloride type salt lake lithium-containing raw brine is more than 20.
Preferably, in the step (1), when the brine is saturated with calcium and calcium chloride crystals are to be separated out, the brine is acidified to remove boron.
Preferably, the pH of the acidified brine in step (1) is 0.5-3.
Further preferably, the pH of the acidified brine in step (1) is 0.5-2.
Preferably, in the step (2), when the brine is naturally evaporated to the calcium content of more than 140g/L, the brine is subjected to calcium freezing and separating operation.
Further preferably, in the step (2), when the brine is naturally evaporated to a calcium content of more than 160g/L, the brine is subjected to calcium freezing and separating operation.
Preferably, in the step (2), the temperature of the brine is reduced to below 15 ℃ by a freezing and crystallizing device.
Further preferably, in the step (2), the temperature of the brine is reduced to below 10 ℃ by a freezing and crystallizing device.
Further preferably, in the step (2), the temperature of the brine is reduced to below 5 ℃ by a freezing and crystallizing device.
Preferably, the freezing and crystallizing device in the step (2) is a cooling crystallizer with a cooling jacket, and a cooling medium is introduced into the cooling jacket.
Preferably, the brine in the step (2) is cooled by using fresh water and/or salt lake raw brine.
Preferably, in the step (2), when the mass concentration of the calcium chloride crystals in the cooling crystallizer is 20-70%, solid-liquid separation is carried out.
Further preferably, in the step (2), when the mass concentration of the calcium chloride crystals in the cooling crystallizer is 25-65%, solid-liquid separation is performed.
Preferably, at least 3 times of natural evaporation-freezing calcium precipitation operations are carried out in the step (2).
Preferably, the mass ratio of Ca/Li in the enriched lithium-enriched brine obtained in step (2) is 10 or less.
Further preferably, the Ca/Li mass ratio in the enriched lithium-enriched brine obtained in the step (2) is 5 or less.
The invention has the beneficial effects that:
(1) the invention adopts the principle that the solubility of calcium chloride is sharply reduced at low temperature, realizes the purpose of separating calcium and lithium from the lithium-containing brine in the salt lake with high calcium-lithium ratio by naturally evaporating, concentrating, cooling, crystallizing and precipitating calcium, and obtains the concentrated brine with low calcium-lithium ratio. The process utilizes the specific climate environment of the lake region, has simple and efficient process, energy conservation and environmental protection, and low cost, effectively solves the technical problem of calcium-lithium separation, and is particularly suitable for extracting lithium from the salt lake brine with high calcium-lithium ratio in areas with poor infrastructure and insufficient energy supply;
(2) compared with the method that the calcium chloride crystals are separated out by utilizing the self environmental temperature difference of day and night in the salt lake area, on one hand, the heat preservation effect of the calcium saturated brine is good after the temperature of the brine is raised in the day, the temperature change from the brine temperature to the night is small, the freezing effect is very poor, and the method is only suitable for freezing in winter; on the other hand, the evaporation amount in winter is very small, so that the improvement of the production efficiency is severely limited. Therefore, the invention cools the brine through the cooling crystallizer with the cooling jacket, thereby achieving the purpose of separating out calcium chloride crystals for many times and obviously improving the production efficiency.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The invention is further described in detail with reference to specific examples, which are exemplified by lithium extraction from Argentina 3Q salt lake brine. In the examples, lithium, calcium, potassium, sodium, magnesium and boron in brine were measured by inductively coupled plasma atomic emission spectrometry (ICP-OES), and chloride ions were measured by silver method.
The following table shows the composition of the raw material salt lake brine
Example 1:
as shown in figure 1, the method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio comprises the following steps:
(1) will be 2000m3(about 2467.4 tons in mass) introducing the raw material salt lake brine into a preconcentration tank, naturally evaporating and concentrating to separate out potassium and sodium mixed salt, beginning to separate out calcium chloride when the calcium content reaches 180g/L, and completing preconcentration to obtain 465m3The calcium saturated brine (about 664.8 tons in mass) is concentrated by 4.1 times compared with the original lithium halide, the Ca/Li basically does not change, the lithium yield is about 96 percent, and the specific content is shown in a table 1-1.
TABLE 1-1 calcium saturated brine ingredient content scale
(2) Introducing calcium saturated brine into an acidification tank, adding hydrochloric acid, and adjusting pH to about 1 to remove boron.
(3) 1 st natural evaporation-freezing calcium separation: introducing acidified brine into a No. 1 calcium chloride pool, and adding Ca in the brine2+When the content reaches about 185g/L, pumping into a No. 1 cooling crystallizer, simultaneously introducing fresh water into a jacket of the crystallizer for cooling, wherein the cooling temperature is 4.5 ℃, and when the solid mass concentration in the crystallizer is about 50%, carrying out solid-liquid separation to finish the 1 st natural evaporation-freezing calcium precipitation to obtain 327.6 tons of 1-time calcium chloride crystals and about 228m of 1-time decalcified brine3(mass about 325.3 tons). Compared with the original lithium halide, the 1-time decalcified brine is concentrated by 7.8 times, the reduction of Ca/Li ratio is 50.5%, the lithium yield is about 89%, and the specific content is shown in tables 1-2.
TABLE 1-21 ingredient content of decalcified bittern
(4) 2 nd natural evaporation-freezing calcium separation: introducing the 1-time decalcified brine into a 2# calcium chloride pool, and naturally evaporating and concentrating to obtain Ca in the brine2+The content reaches about 200g/LPumping into a No. 2 cooling crystallizer, introducing fresh water into a jacket of the crystallizer for cooling at 4.1 deg.C, performing solid-liquid separation when the solid mass concentration in the crystallizer is about 49%, and performing natural evaporation-freezing calcium precipitation for the 2 nd time to obtain 136.1 ton calcium chloride crystal and about 97.5m calcium-removed brine for the 2 nd time3(mass about 139.2 tons). Compared with the original lithium halide, the 2-time decalcified brine is concentrated by 15.7 times, the reduction of Ca/Li ratio is 76.9 percent, the lithium yield is about 76 percent, and the specific content is shown in tables 1-3.
TABLE 1-32 ingredient content of decalcified bittern
(5) 3 rd natural evaporation-freezing calcium separation: introducing the 2-time decalcified brine into a 3# calcium chloride pool, and naturally evaporating and concentrating to obtain Ca in the brine2+When the content reaches about 189g/L, pumping the calcium chloride into a 3# cooling crystallizer, simultaneously introducing fresh water into a jacket of the crystallizer for cooling, wherein the cooling temperature is 4.3 ℃, and when the mass concentration of solids in the crystallizer is about 48 percent, carrying out solid-liquid separation to finish the 3 rd natural evaporation-freezing calcium precipitation to obtain 55.9 tons of calcium chloride crystals for 3 times and about 41.6m of decalcified brine for 3 times3(about 60.5 tons in mass), 30.5 times more concentrated than the original lithium halide, a Ca/Li ratio of 4.85, a reduction of 88.7%, and a lithium yield of about 63%, the specific contents are shown in tables 1-4.
TABLE 1-43 ingredient content of decalcified brine
Pre-concentrating raw brine, acidifying to remove boron, naturally evaporating for 3 times, and freeze-precipitating calcium to obtain concentrated lithium brine of 41.6m3The lithium concentration is reduced to 31.25g/L, Ca/Li ratio to 4.85, the total lithium yield is above 60%, the calcium-lithium separation efficiency is high, and the lithium loss is small.
Example 2:
as shown in figure 1, the method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio comprises the following steps:
(1) will be 2500m3(about 3084.2 tons in mass) introducing the raw material salt lake brine into a preconcentration tank, naturally evaporating and concentrating to separate out potassium and sodium mixed salt, beginning to separate out calcium chloride when the calcium content reaches 160g/L, and finishing preconcentration to obtain 658m3The calcium saturated brine (about 916.6 tons in mass) is concentrated by 3.7 times compared with the original lithium halide, the Ca/Li basically does not change, the lithium yield is about 96.7 percent, and the specific content is shown in a table 2-1.
TABLE 2-1 calcium saturated brine ingredient content scale
(2) Introducing calcium saturated brine into an acidification tank, adding hydrochloric acid, and adjusting pH to about 0.7 to remove boron.
(3) 1 st natural evaporation-freezing calcium separation: introducing acidified brine into a No. 1 calcium chloride pool, and adding Ca in the brine2+When the content reaches about 185g/L, pumping into a No. 1 cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, wherein the cooling temperature is-3.4 ℃, and when the mass concentration of solids in the crystallizer is about 51%, carrying out solid-liquid separation to finish the 1 st natural evaporation-freezing calcium precipitation to obtain 406.7 tons of 1-time calcium chloride crystals and about 276m of 1-time decalcified brine3(mass approx 385.2 tons). Compared with the original lithium halide, the 1-time decalcified brine is concentrated by 8.2 times, the reduction of Ca/Li ratio is 58.9 percent, the lithium yield is about 90 percent, and the specific content is shown in a table 2-2.
TABLE 2-21 ingredient content of decalcified brine
(4) 2 nd natural evaporation-freezing calcium separation: introducing the 1-time decalcified brine into a 2# calcium chloride pond, and adding Ca in the brine2+Pumping into 2# cooling crystallizer when the content reaches about 170g/L, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to-3.4 ℃, and performing solid-liquid separation when the solid mass concentration in the crystallizer is about 41 percent to finish the 2 nd self-purificationThen evaporating and freezing to separate out calcium to obtain 134.7 tons of 2-time calcium chloride crystals and about 142m of 2-time decalcified brine3(the mass is about 197.5 tons), the concentration is 14.4 times of the original lithium halide content, the reduction of Ca/Li ratio is 78.3 percent, the lithium yield is about 81 percent, and the specific content is shown in tables 2-3.
TABLE 2-32 ingredient content of decalcified brine
(5) 3 rd natural evaporation-freezing calcium separation: introducing the 2-time decalcified brine into a 3# calcium chloride pool, and adding Ca in the brine2+When the content reaches about 170g/L, pumping into a 3# cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to-3.4 ℃, performing solid-liquid separation when the mass concentration of solids in the crystallizer is about 41 percent, completing the 3 rd natural evaporation-freezing calcium precipitation to obtain 65.3 tons of 3-time calcium chloride crystals and about 66.9m of 3-time decalcified brine3(about 93.1 tons in mass), 27.2 times more concentrated than the original lithium halide, 89.9% reduction of Ca/Li ratio, about 73% lithium yield, and the specific contents are shown in tables 2-4.
TABLE 2-43 ingredient content of decalcified brine
(6) 4 th natural evaporation-freezing calcium separation: introducing the 3-time decalcified brine into a No. 4 calcium chloride pond, and adding Ca in the brine2+When the content reaches about 140g/L, pumping into a 4# cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to-3.4 ℃, performing solid-liquid separation when the mass concentration of solids in the crystallizer is about 25%, completing the 3 rd natural evaporation-freezing calcium precipitation, and obtaining 19.8 tons of 4-time calcium chloride crystals and about 42.3m of 4-time decalcified brine3(about 60.3 tons in mass), 36.2 times more concentrated than the original lithium halide, a reduction of the Ca/Li ratio of 92.1%, a lithium yield of about 61%, and the specific contents are shown in tables 2-5.
TABLE 2-54 ingredient content of decalcified brine
Pre-concentrating raw brine, acidifying to remove boron, naturally evaporating for 4 times, and freeze-precipitating calcium to obtain lithium concentrated brine 42.3m3The lithium concentration is reduced to 37.11g/L, Ca/Li ratio to 3.41, the total lithium yield is above 60%, the calcium-lithium separation efficiency is high, and the lithium loss is small.
Example 3:
as shown in figure 1, the method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio comprises the following steps:
(1) will be 2500m3(about 3084.2 tons in mass) introducing the raw material salt lake brine into a preconcentration tank, naturally evaporating and concentrating to separate out potassium and sodium mixed salt, beginning to separate out calcium chloride when the calcium content reaches 200g/L, and finishing preconcentration to obtain 528.7m3The calcium saturated brine (about 774.6 tons in mass) is concentrated by 4.6 times compared with the original lithium halide, the Ca/Li basically does not change, the lithium yield is about 96.8 percent, and the specific content is shown in a table 3-1.
TABLE 3-1 calcium saturated brine ingredient content scale
(2) Introducing calcium saturated brine into an acidification tank, adding hydrochloric acid, and adjusting pH to about 0.6 to remove boron.
(3) 1 st natural evaporation-freezing calcium separation: introducing acidified brine into a No. 1 calcium chloride pool, and adding Ca in the brine2+When the content reaches about 215g/L, pumping into a No. 1 cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, wherein the cooling temperature is 7.8 ℃, and when the mass concentration of solids in the crystallizer is about 37.5%, performing solid-liquid separation to finish the 1 st natural evaporation-freezing calcium precipitation to obtain 271.1 tons of 1-time calcium chloride crystals and 1-time calcium chloride crystalsDecalcified brine about 317.6m3(mass approx 385.2 tons). Compared with the original lithium halide, the 1-time decalcified brine is concentrated by 6.9 times, the reduction of Ca/Li ratio is 45.2%, the lithium yield is about 88%, and the specific content is shown in a table 3-2.
TABLE 3-21 ingredient content of decalcified brine
(4) 2 nd natural evaporation-freezing calcium separation: introducing the 1-time decalcified brine into a 2# calcium chloride pond, and adding Ca in the brine2+When the content reaches about 192g/L, pumping into a No. 2 cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to 8.2 ℃, performing solid-liquid separation when the mass concentration of solids in the crystallizer is about 55%, completing natural evaporation-freezing calcium precipitation for the 2 nd time, and obtaining 185.9 tons of 2-time calcium chloride crystals and about 107.4m of 2-time decalcified brine3(about 153.2 tons in mass), the concentration is 17.7 times higher than that of the original lithium halide, the reduction of Ca/Li ratio is 80%, the lithium yield is about 76%, and the specific content is shown in tables 3-3.
TABLE 3-32 ingredient content of decalcified brine
(5) 3 rd natural evaporation-freezing calcium separation: introducing the 2-time decalcified brine into a 3# calcium chloride pool, and adding Ca in the brine2+When the content reaches about 171g/L, pumping into a 3# cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to 7.6 ℃, performing solid-liquid separation when the mass concentration of solids in the crystallizer is about 37 percent, completing the 3 rd natural evaporation-freezing calcium precipitation to obtain 50.9 tons of 3-time calcium chloride crystals and about 59.7m of 3-time decalcified brine3(the mass is about 87.7 tons), the concentration is 28.3 times of the original lithium halide content, the reduction of Ca/Li ratio is 86.5 percent, the lithium yield is about 67.5 percent, and the specific content is shown in a table 3-4.
TABLE 3-43 ingredient content of decalcified brine
(6) 4 th natural evaporation-freezing calcium separation: introducing the 3-time decalcified brine into a No. 4 calcium chloride pond, and adding Ca in the brine2+When the content reaches about 176g/L, pumping into a 4# cooling crystallizer, simultaneously introducing raw brine into a jacket of the crystallizer for cooling, cooling to 7.3 ℃, performing solid-liquid separation when the mass concentration of solids in the crystallizer is about 28%, completing the 3 rd natural evaporation-freezing calcium precipitation, and obtaining 23.1 tons of 4-time calcium chloride crystals and about 40.8m of 4-time decalcified brine3(about 59.8 tons in mass) is 36 times more concentrated than the original lithium halide, the reduction of Ca/Li ratio is 90.7%, the lithium yield is about 58.8%, and the specific content is shown in tables 3-5.
TABLE 3-54 ingredient content of decalcified brine
Pre-concentrating raw brine, acidifying to remove boron, naturally evaporating for 4 times, and freeze-precipitating calcium to obtain 40.8m lithium concentrated brine3The lithium concentration is reduced to 36.89g/L, Ca/Li ratio to 4.0, the total lithium yield is above 58%, the calcium-lithium separation efficiency is high, and the lithium loss is small.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio is characterized by comprising the following steps: the method comprises the following steps:
(1) naturally evaporating the calcium chloride type salt lake lithium-containing raw brine to separate out potassium and sodium mixed salt, and then acidifying the brine to remove boron;
(2) and (2) carrying out natural evaporation-calcium separation freezing operation on the brine treated in the step (1) at least 1 time, wherein the calcium separation freezing operation is to cool the brine to separate out calcium chloride crystals, and then carrying out solid-liquid separation to obtain the concentrated brine enriched with lithium.
2. The method of claim 1, wherein the method comprises the following steps: and (2) acidifying the brine to remove boron when calcium in the brine is saturated and calcium chloride crystals are to be separated out in the step (1).
3. The method of claim 1, wherein the method comprises the following steps: the pH value of the acidified brine in the step (1) is 0.5-3.
4. The method of claim 1, wherein the method comprises the following steps: and (3) in the step (2), when the brine is naturally evaporated until the calcium content is more than 140g/L, performing freezing calcium precipitation operation on the brine.
5. The method of claim 1, wherein the method comprises the following steps: and (3) cooling the brine to below 15 ℃ by using a freezing and crystallizing device in the step (2).
6. The method of claim 5, wherein the method comprises the following steps: the freezing and crystallizing device is a cooling crystallizer with a cooling jacket, and a cooling medium is introduced into the cooling jacket.
7. The method of claim 1, wherein the method comprises the following steps: and (3) cooling the brine in the step (2) by using fresh water and/or salt lake raw brine.
8. The method of claim 6, wherein the method comprises the following steps: and (3) performing solid-liquid separation when the mass concentration of the calcium chloride crystals in the cooling crystallizer is 20-70% in the step (2).
9. The method of claim 1, wherein the method comprises the following steps: and (3) performing natural evaporation-freezing calcium precipitation operation at least in the step (2).
10. The method of claim 1, wherein the method comprises the following steps: the mass ratio of Ca/Li in the enriched lithium concentrated brine obtained in the step (2) is below 10.
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| CN202111374444.8A CN114014340A (en) | 2021-11-19 | 2021-11-19 | Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio |
| PCT/CN2022/111815 WO2023087799A1 (en) | 2021-11-19 | 2022-08-11 | Method for removing calcium-enriched lithium from salt lake brine with high calcium-lithium ratio |
| CL2023000905A CL2023000905A1 (en) | 2021-11-19 | 2023-03-29 | Method to remove calcium and enrich lithium from salt flat brine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114735726A (en) * | 2022-02-28 | 2022-07-12 | 广东邦普循环科技有限公司 | Calcium chloride type lithium-containing salt lake brine evaporation and brine mixing mineralization process |
| CN114906864A (en) * | 2022-06-02 | 2022-08-16 | 紫金矿业集团股份有限公司 | Method for extracting lithium from high-calcium chloride type salt lake brine |
| WO2023087799A1 (en) * | 2021-11-19 | 2023-05-25 | 广东邦普循环科技有限公司 | Method for removing calcium-enriched lithium from salt lake brine with high calcium-lithium ratio |
| CN117327919A (en) * | 2023-09-28 | 2024-01-02 | 中国地质科学院矿产综合利用研究所 | Method for extracting lithium from high-calcium clay type lithium ore |
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| CN108584995B (en) * | 2018-05-28 | 2021-07-09 | 中国地质科学院矿产资源研究所 | Method for comprehensively extracting lithium, potassium and boron from oil field brine |
| CN114014340A (en) * | 2021-11-19 | 2022-02-08 | 广东邦普循环科技有限公司 | Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio |
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- 2021-11-19 CN CN202111374444.8A patent/CN114014340A/en active Pending
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| CN1951817A (en) * | 2006-09-12 | 2007-04-25 | 青海西部矿业科技有限公司 | Method for separating magnesium and enriching lithium from brine of saline lake using high temperature evaporation and crystallization method |
| CN103204523A (en) * | 2012-10-18 | 2013-07-17 | 中国科学院青海盐湖研究所 | Method for preparing lithium salt ore from plateau sulfate type salt lake brine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023087799A1 (en) * | 2021-11-19 | 2023-05-25 | 广东邦普循环科技有限公司 | Method for removing calcium-enriched lithium from salt lake brine with high calcium-lithium ratio |
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| GB2619191B (en) * | 2022-02-28 | 2024-07-31 | Guangdong Brunp Recycling Technology Co Ltd | Process for mineralization from evaporation and brine mixing of calcium chloride-type lithium-containing salt lake brine |
| CN114906864A (en) * | 2022-06-02 | 2022-08-16 | 紫金矿业集团股份有限公司 | Method for extracting lithium from high-calcium chloride type salt lake brine |
| CN117327919A (en) * | 2023-09-28 | 2024-01-02 | 中国地质科学院矿产综合利用研究所 | Method for extracting lithium from high-calcium clay type lithium ore |
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| CL2023000905A1 (en) | 2023-09-08 |
| WO2023087799A1 (en) | 2023-05-25 |
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