CN114906864A - Method for extracting lithium from high-calcium chloride type salt lake brine - Google Patents
Method for extracting lithium from high-calcium chloride type salt lake brine Download PDFInfo
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- 239000012267 brine Substances 0.000 title claims abstract description 119
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 119
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000001110 calcium chloride Substances 0.000 title claims abstract description 56
- 229910001628 calcium chloride Inorganic materials 0.000 title claims abstract description 56
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 66
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 33
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 238000001704 evaporation Methods 0.000 claims abstract description 30
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 18
- 238000004094 preconcentration Methods 0.000 claims abstract description 18
- 239000001103 potassium chloride Substances 0.000 claims abstract description 16
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 12
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- 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
- C01F11/32—Purification
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A method for extracting lithium from high calcium chloride type salt lake brine comprises the following process steps and conditions: pre-concentration: evaporating brine collected from brine collecting well in preconcentration tank under natural condition to sequentially separate out sodium chloride, potassium chloride and carnallite (KCl. MgCl) 2 ) Until the calcium ion concentration of the brine reaches 11-13%; concentration: further carrying out evaporation concentration on the pre-concentrated brine in a concentration tank to separate out calcium chloride crystals until the lithium ion concentration of the brine reaches 3-3.5%; b, extraction and boron removal: removing boron from the concentrated brine by an extraction process; removing calcium and magnesium: removing calcium and magnesium from the brine after boron removal by using sodium hydroxide and sodium carbonate; precipitating lithium by using sodium carbonate: will removeAnd continuously precipitating lithium in the solution after calcium and magnesium by using a sodium carbonate solution, wherein the reaction temperature of lithium precipitation is 70-95 ℃, centrifugally filtering and washing the slurry after lithium precipitation, and finally drying and packaging the washed lithium carbonate to obtain a lithium carbonate product. The method has the advantages of improving the recovery rate of lithium, having smooth process, reducing the production cost, having obvious economic benefit and environmental benefit and the like.
Description
Technical Field
The invention relates to the technical field of lithium extraction from salt lakes, in particular to a method for extracting lithium from high-calcium chloride type salt lake brine.
Background
Lithium and compounds thereof are widely applied to the fields of high-energy batteries, aerospace, nuclear power generation, electronic machinery and the like, and are valuable green resources. Lithium is known as 'white petroleum' and '21-century energy metal', and is one of 24 strategic mineral resources in China.
Lithium resources are mainly present in lithium ores and salt lakes. In addition to lithium ore, 76% of global lithium resources are intensively distributed in salt lakes, and the cost for extracting lithium from the salt lakes is lower than that of extracting lithium from the ore, so that the extraction of lithium from the salt lakes is an important means for solving the shortage of lithium resources.
The common processes for extracting lithium from salt lakes mainly comprise a precipitation method, an adsorption method, a membrane method, an extraction method and the like. The precipitation method is the most mature process for extracting lithium from salt lakes, has low production cost, is mainly used for treating brine with low magnesium-lithium ratio and high lithium concentration, and has the defects of long production period and low lithium recovery rate. The original process flow of the precipitation method is as follows: brine → evaporation concentration → boron removal → calcium and magnesium removal → sodium carbonate precipitation. The adsorption method mainly comprises the steps of selectively adsorbing lithium from brine by using ion exchange resin or ion screen, washing and desorbing to obtain a solution with low impurity content such as magnesium, deeply removing impurities such as boron, calcium, magnesium and the like, concentrating by using a membrane or evaporating and concentrating, and finally precipitating lithium by using sodium carbonate. The adsorption method is mainly used for treating brine with high magnesium-lithium ratio and low lithium concentration, and has large fresh water consumption and high production cost. The membrane method mainly utilizes nanofiltration, reverse osmosis or electrodialysis processes to separate and concentrate impurities to obtain a lithium salt solution with low impurity content, and then utilizes sodium carbonate to precipitate lithium. The membrane method has high automation degree and high production efficiency, but has high fresh water consumption, high installed power and high production cost. The extraction method is to extract and separate lithium from original halogen directly by using an extractant, and to precipitate lithium by using sodium carbonate after a back extraction solution is concentrated. The extraction method has the advantages of short flow and high lithium recovery rate, but has the problems of the performance of an extractant to be improved, organic matter pollution in raffinate and the like, and is generally not suitable for treating brine with high calcium ion content.
For high-calcium chloride type salt lake brine, the production cost is high by adopting an adsorption method and a membrane method, the traditional precipitation method has the problems of poor calcium chloride crystallization effect (the solubility of calcium chloride crystals is sharply increased when the temperature is higher than 25 ℃, the calcium chloride can be dissolved in self crystallization water when the temperature is higher than 30 ℃), low evaporation efficiency and the like in summer, poor extraction selectivity (the extraction capacity of an extractant on calcium is strong) and organic pollution. In addition, the brine exposure process of the traditional precipitation method is adopted, so that the amount of lithium lost in the calcium chloride crystal is large, and the recovery rate of the lithium is low.
The current journals and literature do not report a similar process for extracting lithium from high calcium chloride brine as in the present invention.
Therefore, the method for economically and effectively extracting lithium from the high-calcium chloride type salt lake brine is urgent and has great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for extracting lithium from high-calcium chloride type salt lake brine, which can improve the recovery rate of lithium and ensure a smooth process, can reduce the production cost and has obvious economic and environmental benefits.
The task of the invention is completed by the following technical scheme:
a method for extracting lithium from high-calcium chloride type salt lake brine comprises the following process steps and conditions:
A. pre-concentration: evaporating brine collected from brine collecting well in preconcentration tank under natural condition to sequentially separate out sodium chloride, potassium chloride and carnallite (KCl. MgCl) 2 ) Until the calcium ion of the brine is concentratedThe degree reaches 11-13%;
B. concentration: further carrying out evaporation concentration on the pre-concentrated brine in a concentration tank, and precipitating calcium chloride crystals until the lithium ion concentration of the brine reaches 3-3.5%;
C. b, extraction and boron removal: removing boron from the concentrated brine by an extraction process;
D. calcium and magnesium removal: removing calcium and magnesium from the brine after boron removal by using sodium hydroxide and sodium carbonate; e, precipitating lithium by sodium carbonate: and continuously precipitating lithium in the solution without calcium and magnesium by using a sodium carbonate solution, wherein the reaction temperature of lithium precipitation is 70-95 ℃, centrifugally filtering and washing the slurry after lithium precipitation, and finally drying and packaging the washed lithium carbonate to obtain a lithium carbonate product.
Compared with the prior art, the invention has the following advantages or effects:
(1) the process flow is smooth, and the production efficiency is high. The method is characterized in that different calcium chloride crystallization modes are adopted according to the solubility difference characteristics of calcium chloride crystals in summer and winter, so that the problems that calcium chloride cannot be crystallized in summer and the production efficiency is low are solved, and the overall process is smooth. Meanwhile, calcium chloride crystals are fully utilized to bring away a larger part of water in brine, so that the evaporation speed is increased, and the concentration efficiency of lithium is improved.
(2) The lithium recovery rate is higher. The method is characterized in that the calcium chloride crystals collected by the concentration tank are percolated, and brine carried in the calcium chloride crystals is fully recovered. And (3) carrying out centrifugal filtration and washing on the calcium chloride crystal slurry crystallized in summer, so as to reduce the lithium loss by entrainment to the maximum extent. The lithium recovery rate is effectively improved through the two aspects.
(3) The production cost is low. The method has the advantages that low-temperature brine newly extracted from the brine extraction well is fully utilized as a cold source for cooling and crystallizing the brine in the summer concentration tank, so that the preparation cost of the refrigerant is saved, and the production cost is effectively reduced.
Drawings
FIG. 1 is a process flow diagram of a method for extracting lithium from high-calcium chloride type salt lake brine according to the invention.
The description is described in further detail below with reference to the accompanying drawings.
Detailed Description
As shown in FIG. 1, the method for extracting lithium from high-calcium chloride type salt lake brine of the invention comprises the following process steps and conditions:
A. pre-concentration: evaporating brine collected from brine collecting well in preconcentration tank under natural condition to sequentially separate out sodium chloride, potassium chloride and carnallite (KCl. MgCl) 2 ) Until the calcium ion concentration of the brine reaches 11-13%;
B. concentration: further evaporating and concentrating the pre-concentrated brine in a concentration tank to precipitate calcium chloride crystals until the lithium ion concentration of the brine reaches 3-3.5%;
C. b, extraction and boron removal: removing boron from the concentrated brine by an extraction process;
D. calcium and magnesium removal: removing calcium and magnesium from the brine after boron removal by using sodium hydroxide and sodium carbonate; e, precipitating lithium by sodium carbonate: and continuously precipitating lithium in the solution without calcium and magnesium by using a sodium carbonate solution, wherein the reaction temperature of lithium precipitation is 70-95 ℃, centrifugally filtering and washing the slurry after lithium precipitation, and finally drying and packaging the washed lithium carbonate to obtain a lithium carbonate product.
The process of the invention may further be:
the concentration is carried out according to the solubility difference characteristic of calcium chloride crystals to temperature: naturally evaporating the pre-concentrated brine in a concentration tank to crystallize calcium chloride crystals in winter, stacking the calcium chloride crystals, and percolating brine with high lithium concentration to return to the concentration tank; and in summer, the pre-concentrated brine is cooled and crystallized, the crystallization process of calcium chloride is accelerated to obtain crystal slurry, the crystal slurry is subjected to centrifugal filtration and washing, the filtrate and the washing liquid are returned to a concentration tank, and the washed calcium chloride crystals are stacked in a designated area.
The sodium ion concentration of the brine is controlled to be 0.5-1% at the end point of pre-concentration to separate out sodium chloride, and the calcium ion concentration of the brine is controlled to be 11-13% at the end point of separation of potassium chloride and carnallite.
And in the concentration step, the temperature of the calcium chloride cooling crystallization is controlled to be 5-15 ℃ in summer, and a cold source of the calcium chloride cooling crystallization is low-temperature brine newly extracted from a brine extraction well.
And controlling the lithium ion concentration of the brine to be 3-3.5% at the end point of the calcium chloride crystallization obtained by concentration.
The extractant for extracting and removing boron is isooctanol, and the diluent of the extractant is kerosene.
The ratio (volume ratio of organic phase to water phase) of boron removal by extraction and washing and back extraction is 1.1-1.5, the stirring and mixing time is 3-6 minutes, and the settling time is 30-60 minutes.
The concentration of isooctyl alcohol in the boron-removed by extraction, washing and back-extraction organic phase is 5-20%.
The pH value of the end point of calcium and magnesium removal is controlled to be 10.5-11.5, the amount of sodium carbonate is 1.05-1.3 times of the theoretical amount, and the reaction time is 30-90 minutes.
The amount of the sodium carbonate used for precipitating the lithium by the sodium carbonate is 1.1-1.3 times of the theoretical amount, the reaction temperature is 70-95 ℃, and the reaction time is 30-90 minutes.
And during pre-concentration and concentration, periodically or irregularly collecting salt according to the thickness of the salt in each pool.
Example 1
The main components of a salt lake brine are as follows: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and carnallite are sequentially separated out until the calcium ion concentration of the brine reaches 12 percent. Then pumping the brine into a concentration tank, naturally evaporating and crystallizing calcium chloride crystals in the concentration tank in winter, cooling and crystallizing by using a crystallizer in summer, and taking the newly pumped cold brine as a cold source for cooling and crystallizing at the crystallization temperature of 7 ℃. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and the diafiltered brine is returned to the concentration tank. And cooling the crystallized magma in summer, performing centrifugal filtration and washing, and returning filtrate and washing liquor to a concentration tank. Crystallization in concentration tankThe end point of (3) controls the lithium concentration to 3.2%. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 90 ℃, and the excessive washing of sodium carbonate is 1.15 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is 68%, the evaporation and concentration time of brine is 12 months, and the production cost of lithium carbonate is 19200 yuan/ton.
Example 2
The main components of a salt lake brine are as follows: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and carnallite are sequentially separated out until the calcium ion concentration of the brine reaches 11.5 percent. Then pumping the brine into a concentration tank, naturally evaporating and crystallizing calcium chloride crystals in the concentration tank in winter, cooling and crystallizing by using a crystallizer in summer, and taking the newly pumped cold brine as a cold source for cooling and crystallizing at the crystallization temperature of 14 ℃. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and the diafiltered brine is returned to the concentration tank. And cooling the crystallized crystal mush in summer, carrying out centrifugal filtration and washing, and returning the filtrate and the washing liquid to the concentration tank. The concentration of lithium is controlled to be 3.5% at the end point of crystallization in the concentration tank. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 90 ℃, and the excess amount of sodium carbonate is 1.15 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is 67%, the evaporation and concentration time of brine is 15 months, and the production cost of lithium carbonate is 21000 yuan/ton.
Example 3
The salt lake brine comprises the following main components: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and light brine are sequentially separated outAnd (4) stone until the calcium ion concentration of the brine reaches 12.5%. Then pumping the brine into a concentration tank, naturally evaporating and crystallizing calcium chloride crystals in the concentration tank in winter, cooling and crystallizing by using a crystallizer in summer, and taking the newly pumped cold brine as a cold source for cooling and crystallizing at the crystallization temperature of 10 ℃. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and the diafiltered brine is returned to the concentration tank. And cooling the crystallized crystal mush in summer, carrying out centrifugal filtration and washing, and returning the filtrate and the washing liquid to the concentration tank. The lithium concentration is controlled to be 3.4% at the end point of crystallization in the concentration tank. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, and then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 80 ℃, and the excessive washing of the sodium carbonate is 1.05 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is 62%, the evaporation and concentration time of brine is 13 months, and the production cost of lithium carbonate is 21500 yuan/ton.
Example 4
The main components of a salt lake brine are as follows: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and carnallite are sequentially separated out until the calcium ion concentration of the brine reaches 11.5 percent. Then pumping the brine into a concentration tank, naturally evaporating and crystallizing calcium chloride crystals in the concentration tank in winter, cooling and crystallizing by using a crystallizer in summer, and taking the newly pumped cold brine as a cold source for cooling and crystallizing at the crystallization temperature of 8 ℃. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and the diafiltered brine is returned to the concentration tank. And cooling the crystallized crystal mush in summer, carrying out centrifugal filtration and washing, and returning the filtrate and the washing liquid to the concentration tank. The concentration of lithium is controlled to be 3.0% at the end point of crystallization in the concentration tank. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 75 ℃, and the excess amount of sodium carbonate is 1.10 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is 58 percent, the evaporation and concentration time of brine is 11 months, and the production cost of lithium carbonate22500 yuan/ton.
Comparative example 1
The main components of a salt lake brine are as follows: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and carnallite are sequentially separated out until the calcium ion concentration of the brine reaches 11.5 percent. Then the brine is pumped into a concentration tank, and calcium chloride crystals are naturally evaporated and crystallized in the concentration tank in winter and summer. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and the diafiltered brine is returned to the concentration tank. The lithium concentration is controlled to be 3.2% at the end point of crystallization in the concentration tank. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 90 ℃, and the excessive washing of sodium carbonate is 1.15 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is 51%, the evaporation and concentration time of brine is 18 months, and the production cost of lithium carbonate is 25500 yuan/ton.
Comparative example 2
The main components of a salt lake brine are as follows: li + 0.074％，Na + 6.21％，K + 0.66％，Mg 2+ 0.13％，Ca 2+ 3.26％，Cl - 16.75％，H 3 BO 3 0.56％，SO 4 2- 0.02 percent. The brine extracted from the brine extraction well is firstly put into a preconcentration tank for natural evaporation and concentration, and sodium chloride, potassium chloride and carnallite are sequentially separated out until the calcium ion concentration of the brine reaches 11.5 percent. Then the brine is pumped into a concentration tank, and calcium chloride crystals are naturally evaporated and crystallized in the concentration tank in winter and summer. Calcium chloride crystals withdrawn from the concentration tank are stockpiled in a designated area and brine in the calcium chloride crystals is recovered without percolation. The concentration of lithium is controlled to be 3.2% at the end point of crystallization in the concentration tank. The concentrated brine is sequentially extracted to remove boron, calcium and magnesium, then lithium is precipitated by using a sodium carbonate solution, the reaction temperature is 80 ℃, and the excessive washing of sodium carbonate is 1.15 times of the theoretical amount. The comprehensive recovery rate of lithium in the whole process is46 percent, the evaporation and concentration time of the brine is 18 months, and the production cost of the lithium carbonate is 27000 yuan/ton.
The main parameters and technical indices of the examples and comparative examples are compared in the following table.
As described above, the present invention can be preferably realized. The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (11)
1. The method for extracting lithium from high-calcium chloride type salt lake brine is characterized by comprising the following process steps and conditions:
A. pre-concentration: evaporating brine collected from brine collecting well in preconcentration tank under natural condition to sequentially separate out sodium chloride, potassium chloride and carnallite (KCl. MgCl) 2 ) Until the calcium ion concentration of the brine reaches 11-13%;
B. concentration: further carrying out evaporation concentration on the pre-concentrated brine in a concentration tank to separate out calcium chloride crystals until the lithium ion concentration of the brine reaches 3-3.5%;
C. b, extraction and boron removal: removing boron from the concentrated brine by an extraction process;
D. removing calcium and magnesium: removing calcium and magnesium from the brine after boron removal by using sodium hydroxide and sodium carbonate;
E. precipitating lithium by using sodium carbonate: and continuously precipitating lithium in the solution without calcium and magnesium by using a sodium carbonate solution, wherein the lithium precipitation reaction temperature is 70-95 ℃, centrifugally filtering and washing the slurry after lithium precipitation, and finally drying and packaging the washed lithium carbonate to obtain a lithium carbonate product.
2. The method as set forth in claim 1, wherein said concentrating is based on the solubility difference characteristics of calcium chloride crystals with respect to temperature: naturally evaporating the pre-concentrated brine in a concentration tank to crystallize calcium chloride crystals in winter, stacking the calcium chloride crystals, and percolating brine with high lithium concentration to return to the concentration tank; and in summer, the pre-concentrated brine is cooled and crystallized, the crystal mush obtained by crystallization in the crystallization process of calcium chloride is quickened to be centrifugally filtered and washed, the filtrate and the washing liquid are returned to a concentration tank, and the washed calcium chloride crystals are stacked in a designated area.
3. The method of claim 1, wherein the preconcentration is performed to control the sodium ion concentration of the brine to 0.5-1%, and the potassium chloride and carnallite to 11-13%.
4. The method of claim 1, wherein the concentration is carried out by controlling the temperature of the calcium chloride cooling crystallization to be 5-15 ℃ in summer, and the cold source of the calcium chloride cooling crystallization is low-temperature brine newly extracted from a brine extraction well.
5. The method according to claim 1, 3 or 4, wherein the concentration of lithium ions in the brine at the end point of the calcium chloride crystal precipitation is controlled to be 3-3.5%.
6. The method of claim 1, wherein the extractant for extracting boron is isooctanol and the diluent for the extractant is kerosene.
7. The method as set forth in claim 1, characterized in that the phase ratio (volume ratio of organic phase to aqueous phase) of the boron removal by extraction and washing and back-extraction is 1.1-1.5, the stirring and mixing time is 3-6 minutes, and the settling time is 30-60 minutes.
8. The method as claimed in claim 1, 6 or 7, wherein the concentration of isooctanol in the organic phase of the extraction boron removal, washing and stripping is 5-20%.
9. The method as claimed in claim 1, wherein the end point of calcium and magnesium removal is controlled to have a pH value of 10.5 to 11.5, the amount of sodium carbonate is 1.05 to 1.3 times of the theoretical amount, and the reaction time is 30 to 90 minutes.
10. The method as claimed in claim 1, wherein the amount of sodium carbonate used for precipitating lithium carbonate is 1.1-1.3 times of the theoretical amount, the reaction temperature is 70-95 ℃, and the reaction time is 30-90 minutes.
11. The method as claimed in claim 1, wherein the pre-concentration and concentration are performed periodically or non-periodically depending on the thickness of salt in the respective cell.
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