CN115786734B - Method for recovering lithium by concentrating crystalline salt of brine - Google Patents
Method for recovering lithium by concentrating crystalline salt of brine Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 145
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000012267 brine Substances 0.000 title claims abstract description 31
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 238000001035 drying Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000000110 cooling liquid Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 239000007921 spray Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 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 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004094 preconcentration Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
The invention discloses a method for recovering lithium from concentrated crystalline salt of brine, which comprises the steps of adopting materials (post-sun-curing salt liquid) in a cooled system to carry out slurry mixing, spray washing on the concentrated crystalline salt, filtering after washing, and enabling the washed liquid to enter a first-stage salt-curing pond in a salt-curing two-stage; and then, spraying and washing the crystallized salt filter cake washed by the first liquid of the solar salt, and enabling the washed liquid to enter a first-stage solar salt pond of a second stage of the solar salt so as to further reduce the loss of lithium carried by the crystallized salt. The process provided by the invention is simple and convenient; in the washing stage, the salt is slightly reversely dissolved, so that the burden of a salt-drying pond is not obviously increased, and the recovery rate and the productivity of lithium are obviously improved.
Description
Technical Field
The invention relates to the technical field of salt lake lithium extraction, in particular to a method for recovering lithium by concentrating crystalline salt of brine.
Background
Lithium is known as "21 st century energy metal", and with the rapid development of new energy automobiles and electronic devices, the demand of people for lithium has been rising year by year. The lithium content in the crust is only around 0.0065%, a small part of which is present in the rock deposit, whereas about 80% of the lithium resources are contained in the salt lake brine. Aiming at the occurrence state and characteristics of salt lake brine lithium resources, the salt lake lithium extraction technology which is successful at present comprises a salt pan concentration precipitation method, a membrane method, an extraction method, an adsorption method and the like. The salt pan concentration and precipitation method is a mainstream salt lake lithium extraction process with highest application capacity at present, and the process flow is shown in figure 1. For example, salt field concentration and precipitation processes are used for the development of the Chilean Atacama lake, the American silver Peak (USA), and the Argentina Olaroz salt lake.
The salt field concentration and precipitation process is to naturally evaporate and concentrate salt lake brine by utilizing solar energy, firstly, the brine passes through a solar salt first-stage multistage evaporation pond (also called solar salt pond) to remove sodium and potassium, sodium and potassium salts (solar salt first-crystal salt) are produced, a solar salt first-stage liquid (namely pre-concentrate) is obtained, then the solar salt second-stage multistage evaporation pond is used for concentrating, calcium and/or magnesium chloride crystal salts (namely solar salt second-crystal salt) are separated out, a solar salt second-stage liquid (namely concentrate) is obtained, and then the lithium chloride purified liquid is obtained after purification and impurity removal, and then a lithium product is prepared by a sodium carbonate precipitation method. The process is mature, simple to operate and high in reliability. However, in the salt pan concentration process, loss such as salt pan leakage and crystalline salt entrainment is caused, especially in the salt drying stage, calcium or magnesium chloride needs to be concentrated to a higher concentration to be crystallized and separated out, so that the lithium entrainment loss of the crystalline salt is remarkable (the average recovery rate of lithium in the salt pan in south America is lower than 35 percent at present).
In order to improve the lithium recovery rate of the salt-drying process and reduce the system loss, chinese patent application CN115011816a reports a method for recovering lithium from calcium chloride crystals in a salt field, firstly, the calcium chloride crystals produced in a brine concentrating stage (i.e. the salt-drying stage in fig. 1) are subjected to percolation and crushing, and then the brine in a pre-concentrating tank is used for stirring and washing the calcium chloride crystals, so as to realize the method for recovering lithium in the brine concentrating and crystallizing. However, the recovery rate of lithium and the back dissolution of calcium salt in the process are closely related to the concentration of lithium and calcium in a concentration tank, brine with a small concentration degree (the concentration of Li and Ca in brine is relatively low) in a pre-concentration stage (i.e. a first stage of salt sunning in FIG. 1) is adopted as washing water, the recovery rate of lithium is relatively high, and the back dissolution of calcium salt is relatively high; in contrast, brine with larger concentration degree in the pre-concentration stage is adopted, and the calcium salt is reversely dissolved, but the recovery rate of lithium is relatively low. Therefore, a method for recovering lithium from concentrated brine crystals is needed to be developed, which not only can obtain higher lithium recovery rate, but also can avoid the reverse dissolution of calcium or magnesium chloride crystals during washing so as to realize open circuit of crystal salts.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for recovering lithium by concentrating crystalline salt of brine.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for recovering lithium by concentrating crystalline salt of brine, comprising the following steps:
step one, brine is subjected to salt burning by adopting a salt pan concentration and precipitation process, and then a second salt burning solution obtained in the salt pan concentration and precipitation process is further cooled and crystallized; mixing and pulping the bottom flow slurry of the crystallizer with the solar salt di-crystal salt obtained in the salt pan concentration and precipitation process, determining whether the cooled solar salt one-back liquid obtained in the salt pan concentration and precipitation process needs to be supplemented according to the concentration of the ore slurry, and controlling the mass concentration of the ore slurry to be 40-55%;
step two, filtering the pulp after pulp mixing, and returning filtrate to a first-stage salt-sunning pond of a salt-sunning two-stage salt-sunning process of a salt field concentration and precipitation process;
and thirdly, cooling the first-stage salt-drying liquid obtained in the salt pan concentration and precipitation process to 0-10 ℃, and spraying and washing the crystalline salt filter cake as washing water of the crystalline salt filter cake obtained in the second-stage filtering, wherein the washing liquid enters a first-stage salt-drying pond of the salt-drying two stage.
Further, in the first step, the crystallization temperature of the liquid cooling after salt drying is 0-15 ℃ and the time is 0.5-24 hours.
Further, in the first step, for the brine of a calcium salt system, the concentration of calcium ions in the cooled post-sun-dried salt solution is 140-200g/L; for the brine of the magnesium salt system, the concentration of magnesium ions in the cooled post-sun-curing salt solution is 100-140g/L.
In the first step, the mixing and size mixing are carried out under the stirring condition, the stirring linear speed is 0.5-3m/s, and the stirring time is 2-30min.
In the second step, the filtration is carried out in a centrifugal mode, the centrifugal force is controlled to be 400-700G, and the centrifugal time is controlled to be 1-10min.
Further, in the third step, a cooled solar salt post-liquid is adoptedSpray washing the crystalline salt filter cake, wherein the weight ratio of the washing liquid volume to the crystalline salt filter cake is ml/g or m 3 And/t is 0.1-0.4.
Further, the method comprises the following steps: and (3) washing the crystallized salt filter cake washed in the third step by adopting clear water, and enabling the washed liquid to enter a first-stage salt-airing pond of a salt-airing stage, and conveying the washed crystallized salt to a salt field for stockpiling or recycling.
Further, in the fourth step, the ratio of the washing liquid volume to the weight of the crystalline salt cake, ml/g or m 3 And/t is 0.01-0.05.
The invention has the beneficial effects that:
1) According to the invention, the first sunburn salt liquid is used as washing water, and after being cooled to 0-10 ℃, calcium or magnesium is close to saturation under the condition of relatively low lithium concentration, so that a large amount of re-dissolution of the second sunburn salt crystal salt in the washing process can be avoided, and the open circuit of the crystal salt is not influenced;
2) The lithium concentration in the washed liquid obtained by the method is relatively high, and the washed liquid can directly enter a first-stage salt-sunning pond of a salt-sunning stage, so that the salt-sunning concentration time of a salt field is further shortened;
3) The invention adopts a centrifugal washing mode, which can obviously reduce the halogen content of salt in the filtration and washing processes, and further improve the washing efficiency and comprehensive recovery rate of lithium;
4) The invention adopts a small amount of clear water to spray and wash the crystallized salt filter cake washed by the liquid after the salt is dried, thereby further reducing the loss of lithium carried by the crystallized salt;
5) The invention adopts cooled low-lithium but near-saturated calcium or magnesium chloride post-sun salt solution to carry out size mixing, spraying and washing, and further adopts a small amount of clean water to carry out washing, thus the process is simple and convenient; in the washing stage, the salt is slightly reversely dissolved, so that the burden of a salt-drying pond is not obviously increased, and the recovery rate and the productivity of lithium are obviously improved; the invention can effectively improve the technical and economic indexes in the high-calcium or magnesium salt lake brine salt-burning process.
Drawings
FIG. 1 is a schematic diagram of a conventional salt pan concentration and precipitation process flow;
FIG. 2 is a flow chart of the method in examples 1-6 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that, while the present embodiment provides a detailed implementation and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
Taking high-calcium brine (Li 1g/L, ca g/L, na g/73 g/L, K8.64.64 g/L, mg1.78g/L, cl g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid of the dried salt is further cooled and crystallized at the temperature of 10 ℃ for 10 hours; the crystallizer underflow and the solar salt bicrystal salt (both of which are decalcified crystal salts, mainly CaCl) 2 ·6H 2 O+CaCl 2 ·4H 2 Mixing O) with a salt-drying first-later liquid (Li concentration is 4.07 g/L) at 10 ℃ for size mixing, controlling the pulp concentration to be 40%, and stirring at a linear speed of 2m/s for 5min; subsequently, centrifugal filtration was performed, and the centrifugal force was 570G for 5min. And after the filtration is finished, taking a first liquid of sun-dried salt at 10 ℃ and carrying out centrifugal spray washing on the obtained crystalline salt filter cake, wherein the washing ratio is 0.4, and the final washing liquid (filtrate+washing water) is sent for inspection. The result shows that after the calcium salt is subjected to size mixing and spray washing by the first liquid after salt drying, the recovery rate of Li reaches 73.1 percent, the concentration of Li in the washing liquid is 6.01g/L, the washing liquid can return to the first-stage salt drying pond in the salt drying stage, and the dissolution rate of the calcium salt is about 1.1 percent.
Example 2
Taking high-calcium brine (Li 1g/L, ca g/L, na g/73 g/L, K8.64.64 g/L, mg1.78g/L, cl g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid of the dried salt is further cooled and crystallized at the temperature of 7 ℃ for 10 hours; the crystallizer underflow and the solar salt bicrystal salt (both of which are decalcified crystal salts, mainly CaCl) 2 ·6H 2 O+CaCl 2 ·4H 2 Mixing O) with a salt-drying first-later liquid (Li concentration is 3.78 g/L) at 7 ℃ for size mixing, controlling the pulp concentration to be 55%, and stirring at a linear speed of 2m/s for 5min; subsequently, centrifugal filtration is carried out, centrifugal force 570G, wherein the time is 5min; and after the filtration is finished, taking a post-sun-dried salt solution at 7 ℃ to centrifugally spray and wash the obtained crystalline salt filter cake, wherein the washing ratio is 0.2, and the final washing solution (filtrate+washing water) is sent for inspection. The result shows that after the calcium salt is subjected to size mixing and spray washing by the first liquid after salt drying, the recovery rate of Li reaches 69.9%, the concentration of Li in the washing liquid is 6.93g/L, the washing liquid can return to the first-stage salt drying pond in the salt drying stage, and the dissolution rate of the calcium salt is about 0.4%.
Example 3
Taking high-calcium brine (Li 1g/L, ca g/L, na g/73 g/L, K8.64.64 g/L, mg1.78g/L, cl g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid of the dried salt is further cooled and crystallized at the temperature of 7 ℃ for 10 hours; the crystallizer underflow and the solar salt bicrystal salt (both of which are decalcified crystal salts, mainly CaCl) 2 ·6H 2 O+CaCl 2 ·4H 2 Mixing O) with a salt-drying first-later liquid (Li concentration is 3.78 g/L) at 7 ℃ for size mixing, controlling the pulp concentration to be 55%, and stirring at a linear speed of 2m/s for 5min; subsequently, centrifugal filtration was performed, with a centrifugal force of 570G for 5min; after the filtration is finished, taking a salt-drying post-solution at 7 ℃ to centrifugally spray and wash the obtained crystalline salt filter cake, wherein the washing ratio is 0.2; and then, taking clear water again for centrifugal spray washing, wherein the washing ratio is 0.03, and the final washing liquid (filtrate and washing water) is sent for inspection. The result shows that after the calcium salt is slurried by the first post-sun-salt solution and the crystallization salt filter cake is sprayed and washed by the first post-sun-salt solution and clear water, the recovery rate of Li reaches 79.2 percent, the concentration of Li in the washing liquid is 6.33g/L, the washing liquid can return to the first stage sun-salt pond in the second sun-salt stage, and the dissolution rate of the calcium salt is about 12.5 percent.
Example 4
Taking brine (Li 0.638g/L, na 93.87g/L, K15.432.432 g/L, mg 17.312g/L, cl 193.069 g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid after salt drying is further cooled and crystallized at the temperature of 10 ℃ for 10 hours; then the bottom flow slurry of the crystallizer and the salt-drying bicrystal salt (the two are magnesium-removing crystallization salt, mainly KCl-MgCl) 2 ·6H 2 O+MgCl 2 ·6H 2 O) in a post-sun-salt solution (Li concentration: 2.8 g/L)Mixing and pulping at 10 ℃, controlling the concentration of ore pulp to be 40%, and stirring for 5min at the linear speed of 2 m/s; subsequently, centrifugal filtration was performed, with a centrifugal force of 570G for 4min; after the filtration, the obtained crystalline salt filter cake was centrifugally spray washed with a washing ratio of 0.4 by taking a post-sun-dried salt solution at 10℃and the final washing solution (filtrate+washing water) was sent for inspection. The result shows that after the magnesium salt is subjected to size mixing and spray washing by the first liquid after salt drying, the recovery rate of Li reaches 79.4%, the concentration of Li in the washing liquid is 3.59g/L, the washing liquid can return to the first-stage salt drying pond in the salt drying stage, and the dissolution rate of the magnesium salt is about 2.1%.
Example 5
Taking brine (Li 0.638g/L, na 93.87g/L, K15.432.432 g/L, mg 17.312g/L, cl 193.069 g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid after salt drying is further cooled and crystallized at the temperature of 7 ℃ for 10 hours; then the bottom flow slurry of the crystallizer and the salt-drying bicrystal salt (the two are magnesium-removing crystallization salt, mainly KCl-MgCl) 2 ·6H 2 O+MgCl 2 ·6H 2 Mixing O) with a salt-drying first-later liquid (Li concentration is 2.78 g/L) at 7 ℃ for size mixing, controlling the pulp concentration to be 55%, and stirring at a linear speed of 2m/s for 5min; subsequently, centrifugal filtration was performed, with a centrifugal force of 570G for 4min; after the filtration, the obtained crystalline salt filter cake was subjected to centrifugal spray washing with a washing ratio of 0.2 in a post-sun-salt solution at 7℃and the final washing solution (filtrate+washing water) was sent for inspection. The result shows that after the magnesium salt is subjected to size mixing and spray washing by the first liquid after salt drying, the recovery rate of Li reaches 70.1 percent, the concentration of Li in the washing liquid is 4.34g/L, the washing liquid can return to the first-stage salt drying pond in the salt drying stage, and the dissolution rate of the magnesium salt is about 1.0 percent.
Example 6
Taking brine (Li 0.638g/L, na 93.87g/L, K15.432.432 g/L, mg 17.312g/L, cl 193.069 g/L) as an example, as shown in FIG. 2, after salt is dried by adopting a salt pan concentration and precipitation process, the second liquid after salt drying is further cooled and crystallized at the temperature of 7 ℃ for 10 hours; then the bottom flow slurry of the crystallizer and the salt-drying bicrystal salt (the two are magnesium-removing crystallization salt, mainly KCl-MgCl) 2 ·6H 2 O+MgCl 2 ·6H 2 O) and sun-dried saltMixing the post-liquid (Li concentration is 2.78 g/L) at 7 ℃ for pulp mixing, controlling the pulp concentration to be 55%, and stirring for 5min at the linear speed of 2 m/s; subsequently, centrifugal filtration was performed, with a centrifugal force of 570G for 4min; after the filtration is finished, taking a salt-drying post-liquid at 7 ℃ to centrifugally spray and wash the obtained crystalline salt filter cake, wherein the washing ratio is 0.2; and then, taking clear water again for centrifugal spray washing, wherein the washing ratio is 0.03, and the final washing liquid (filtrate and washing water) is sent for inspection. The result shows that after the magnesium salt is slurried by the first post-sun-curing liquid and the crystallization salt filter cake is sprayed and washed by the first post-sun-curing liquid and clear water, the recovery rate of Li reaches 82.5 percent, the concentration of Li in the washing liquid is 3.87g/L, the washing liquid can return to the first salt curing pond in the second salt curing stage, and the dissolution rate of the magnesium salt is about 11.3 percent.
The main parameters and technical indices of each example are shown in table 1.
TABLE 1
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (7)
1. A method for recovering lithium by concentrating crystalline salt of brine, which is characterized by comprising the following steps:
step one, brine is subjected to salt burning by adopting a salt pan concentration and precipitation process, and then a second salt burning solution obtained in the salt pan concentration and precipitation process is further cooled and crystallized; mixing and pulping the bottom flow slurry of the crystallizer with the solar salt di-crystal salt obtained in the salt pan concentration and precipitation process, determining whether the cooled solar salt one-back liquid obtained in the salt pan concentration and precipitation process needs to be supplemented according to the concentration of the ore slurry, and controlling the mass concentration of the ore slurry to be 40-55%;
step two, filtering the pulp after pulp mixing, and returning filtrate to a first-stage salt-sunning pond of a salt-sunning two-stage salt-sunning process of a salt field concentration and precipitation process;
step three, cooling the first post-sun salt liquid obtained in the salt pan concentration and precipitation process to 0-10 ℃, and spraying and washing the crystalline salt filter cake as washing water of the crystalline salt filter cake obtained in the step two, wherein the washing liquid enters a first-stage salt sun pond of a salt sun drying stage;
step four: and (3) washing the crystallized salt filter cake washed in the third step by adopting clear water, and enabling the washed liquid to enter a first-stage salt-airing pond of a salt-airing stage, and conveying the washed crystallized salt to a salt field for stockpiling or recycling.
2. The method according to claim 1, wherein in the first step, the crystallization temperature of the liquid after the salt drying is between 0 and 15 ℃ for 0.5 to 24 hours.
3. The method according to claim 1, wherein in the first step, for the brine of the calcium salt system, the calcium ion concentration in the post-sun-dried salt-post-cooling liquid is 140-200g/L; for the brine of the magnesium salt system, the concentration of magnesium ions in the cooled post-sun-curing salt solution is 100-140g/L.
4. The method according to claim 1, wherein in the first step, the mixing and pulping are performed under stirring conditions, and the stirring linear speed is 0.5-3m/s, and the stirring time is 2-30min.
5. The method according to claim 1, wherein in the second step, the filtration is performed by centrifugation, the centrifugal force is controlled to be 400-700G, and the centrifugation time is 1-10min.
6. The method according to claim 1, wherein in step three, the crystalline salt cake is spray-washed with a cooled post-sun-salt solution, the ratio of washing liquid volume to crystalline salt cake weight ml/g or m 3 And/t is 0.1-0.4.
7. The method according to claim 1, wherein in step four, the ratio of washing liquid volume to weight of crystalline salt cake is ml/g or m 3 And/t is 0.01-0.05.
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Citations (7)
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