CN213113446U - Device for extracting lithium from salt lake - Google Patents
Device for extracting lithium from salt lake Download PDFInfo
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- CN213113446U CN213113446U CN202021477460.0U CN202021477460U CN213113446U CN 213113446 U CN213113446 U CN 213113446U CN 202021477460 U CN202021477460 U CN 202021477460U CN 213113446 U CN213113446 U CN 213113446U
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Abstract
The utility model relates to a device for extracting lithium from salt lake, which is a membrane concentration device (4) connected with an adsorption device (2) and used for concentrating desorption liquid obtained from the adsorption device (2); a purification resin column (5) connected to the concentration side of the membrane concentration device (4) and used for removing calcium and magnesium from the concentrated solution obtained in the membrane concentration device (4); the bipolar membrane device (6) is connected with the purification resin column (5) and is used for electrolyzing the purified lithium-rich solution obtained in the purification resin column (5); and the evaporative crystallizer (7) is connected with the alkali chamber of the bipolar membrane device (6) and is used for carrying out concentration crystallization treatment on the solution containing the lithium hydroxide obtained in the alkali chamber. The utility model discloses with absorption method coupling embrane method, utilize carbonate type salt lake brine to prepare out lithium hydrate, and have simple process, economic nature is good, and the lithium yield is high, and it is short to carry the lithium cycle, and is friendly to the environment, and is pollution-free, advantages such as serialization production can be carried out.
Description
Technical Field
The utility model relates to a method for extracting lithium from salt lake brine, in particular to a method for extracting lithium hydroxide from carbonate type salt lake brine.
Background
Lithium is an important strategic resource substance and is an indispensable important raw material of modern high-tech products. With the wide application of lithium and lithium salt and the continuous development of high and new technology, especially the rapid development of lithium battery industry in recent years, the demand of the market for lithium is rapidly increased. At present, lithium salt is mostly extracted from the ore in China, but with the continuous reduction of high-grade lithium ore and the continuous improvement of the cost of extracting lithium from the ore, and because the salt lake is rich in a large amount of lithium elements, the lithium extraction from the salt lake gradually draws attention of people.
China has huge lithium resource reserves, is second to Vivia only and is located in the second position in the world. The Tibet of China has rich lithium resources in the hydrochloride salt lakes, and the famous carbonate salt lakes comprise Bangkong, Dangzongiao, Zabuye tea card, Guogaline and the like, wherein the Zabuye salt lake is the first and third salt lakes in China, and the lithium carbonate reserve is about 184 ten thousand tons. Carbonate type lithium salt lake due to CO existing in large amount in brine3 2-Limit Ca2+、Mg2+The concentration range of the salt lake exists in the brine, so that the small magnesium-lithium ratio of the brine is created, and the carbonate salt lake is used for extracting lithium from the brineAnd (4) high-quality resources.
At present, a gradient solar cell process is adopted for extracting lithium from a carbonate salt lake, and patent CN1398786A provides a method for extracting lithium carbonate from carbonate salt lake brine by crystallizing and separating out the lithium carbonate from the carbonate salt lake brine by using solar energy and taking an solar cell as a crystallization cell. The method has the advantages of simple operation and low cost, but has the problems of low lithium yield, need of constructing a salt field, long lithium extraction period, low product purity, difficulty in quickly expanding the productivity and the like.
As a novel technology for extracting lithium from salt lakes, the adsorption method has the characteristics of high lithium extraction efficiency, low use cost, strong environmental protection advantage and the like. The current adsorption method only uses chloride brine and sulfate brine, the system is single, and most of lithium-rich solution is used for preparing lithium carbonate and lithium chloride products. Patent CN1511964A discloses an adsorption method for extracting lithium from salt lake brine, which is simple in process flow and environment-friendly, but is only suitable for the concentrated lithium-containing old brine in Qinghai salt lake brine and salt pan, and the obtained lithium-rich solution is used for preparing lithium carbonate and lithium chloride.
SUMMERY OF THE UTILITY MODEL
The utility model provides a method for extracting lithium hydroxide from carbonate type salt lake brine. The utility model discloses with absorption method coupling embrane method, utilize carbonate type salt lake brine to prepare out lithium hydrate, and have simple process, economic nature is good, and the lithium yield is high, and it is short to carry the lithium cycle, and is friendly to the environment, and is pollution-free, advantages such as serialization production can be carried out.
A process for extracting lithium from a salt lake is applied to carbonate brine and comprises the following steps:
step 1, adsorbing brine by using a lithium adsorbent, and desorbing the adsorbent by using a desorbent to obtain a desorption solution;
step 2, concentrating the desorption solution obtained in the step 1 to obtain a concentrated solution;
step 4, carrying out bipolar membrane electrolysis treatment on the purified lithium-rich solution obtained in the step 3 to obtain an acid solution and an alkali solution;
and 5, crystallizing the alkali solution obtained in the step 4 to obtain lithium hydroxide and crystallization mother liquor.
In one embodiment, in the step 1, the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions and chloride ions in the salt lake brine are 0.1-10g/L, 10-150g/L, 0.01-1g/L, 0.1-4g/L, 5-50g/L and 20-150g/L respectively.
In one embodiment, the brine in step 1 is pretreated to remove suspended matters.
In one embodiment, filtering out the suspended matter means filtering with a medium filter or a membrane filter.
In one embodiment, the membrane filter is a microfiltration membrane or an ultrafiltration membrane;
in one embodiment, the membrane filter is a hollow fiber, tubular or multi-channel membrane element.
In one embodiment, the membrane filter is of a structure comprising: the ceramic membrane component is provided with two ends with end sockets, a material inlet and a material outlet are respectively arranged on the end sockets, and a penetrating fluid outlet is also arranged on the ceramic membrane component; the ceramic membrane module is characterized in that a ceramic membrane tube is arranged inside the ceramic membrane module, a conical membrane tube inlet joint is arranged at one end, facing the material inlet, of the ceramic membrane tube, one side of a conical large cross section faces the material inlet, and an inner wall spiral groove is formed in the wall surface of the inner part, facing the material inlet, of the membrane tube inlet joint.
In one embodiment, in the step 2, at least one of a titanium-based adsorbent and a manganese-based adsorbent is adsorbed.
In one embodiment, in the step 2, the desorbent is an acid solution with a hydrogen ion concentration of 0.01-1 mol/L.
In one embodiment, in step 2, the acid solution is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
In one embodiment, the acid solution obtained in the step 5 is subjected to concentration adjustment and then sent to the step 2 to be used as a desorbent to desorb the adsorbent.
In one embodiment, in the step 2, the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 0.5-5.0 g/L, 0.1-5.0 g/L, 0-0.05 g/L and 0-0.05 g/L respectively; the pH value of the desorption liquid is 1-7, and preferably 3-7.
In one embodiment, in step 3, the concentration is performed by membrane concentration; one or more of reverse osmosis membrane, forward osmosis membrane, electrodialysis membrane, and DTRO membrane may be used.
In one embodiment, in the step 3, the concentration of lithium ions, sodium ions, calcium ions and magnesium ions in the obtained concentrated solution is 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.8 g/L and 0-0.8 g/L respectively.
In one embodiment, in the step 4, the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the purified lithium-rich solution are respectively 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.005 g/L and 0-0.005 g/L.
In one embodiment, in the step 5, the concentration of hydrogen ions in the acid solution is 1.0 to 2.5 mol/L; the concentration of lithium ions in the alkali solution is 1.0-2.5 mol/L.
An apparatus for extracting lithium from a salt lake, comprising:
the adsorption device is used for carrying out lithium ion adsorption treatment on the brine;
the membrane concentration device is connected with the adsorption device and is used for concentrating desorption liquid obtained in the adsorption device;
the purification resin column is connected to the concentration side of the membrane concentration device and is used for removing calcium and magnesium from the concentrated solution obtained in the membrane concentration device;
the bipolar membrane device is connected with the purification resin column and is used for electrolyzing the purified lithium-rich solution obtained from the purification resin column;
and the evaporative crystallizer is connected with the alkali chamber of the bipolar membrane device and is used for carrying out concentration crystallization treatment on the solution containing the lithium hydroxide obtained in the alkali chamber.
In one embodiment, further comprising: the prefilter is used for prefiltering brine, and the adsorption device is connected to the prefilter.
In one embodiment, the prefilter is a filter using a screen, a grate, a plate frame, a media filter, or a membrane filter.
In one embodiment, the membrane filter is provided with a hollow fiber type, tubular type or multi-channel type membrane element.
In one embodiment, the membrane filter is a microfiltration or ultrafiltration membrane.
In one embodiment, the structure of the membrane filter comprises a ceramic membrane component, wherein end sockets are arranged at two ends of the ceramic membrane component, a material inlet and a material outlet are respectively arranged on the end sockets, and a penetrating fluid outlet is also arranged on the ceramic membrane component; the ceramic membrane module is characterized in that a ceramic membrane tube is arranged inside the ceramic membrane module, a conical membrane tube inlet joint is arranged at one end, facing the material inlet, of the ceramic membrane tube, one side of a conical large cross section faces the material inlet, and an inner wall spiral groove is formed in the wall surface of the inner part, facing the material inlet, of the membrane tube inlet joint.
In one embodiment, the adsorption device is filled with an adsorbent for adsorbing lithium ions.
In one embodiment, the adsorbent is at least one of a titanium-based adsorbent or a manganese-based adsorbent.
In one embodiment, the adsorption device is provided with a desorbent feeding pipe for feeding the desorbent into the adsorption device.
In one embodiment, further comprising: and the acid adjusting tank is used for adjusting the pH of the acid solution obtained in the bipolar membrane device and desorbing the acid solution by using the adsorption device.
In one embodiment, the membrane concentration device is one or more of a reverse osmosis membrane, a forward osmosis membrane, an electrodialysis membrane and a DTRO membrane.
Advantageous effects
The process of the utility model can directly prepare lithium hydroxide from carbonate type brine.
The utility model discloses an adopted bipolar membrane's electrolytic treatment in the technology, can directly obtain lithium hydroxide, avoided traditional method to need add the mode that carbonate formed lithium carbonate and deposite, it is good to have the production continuity, advantage that product purity is high.
The utility model discloses do not need to construct the salt pan and shine steamed, not only shortened and carried the lithium cycle, avoided moreover shining steamed in-process brine infiltration or salt crystallization smuggleing the lithium yield that the lithium salt problem leads to low. In addition, the utility model discloses can continuous automated production, easily expand the productivity.
The utility model treats carbonate brine which contains more carbonate ions and adopts an alkaline environment when the adsorbent is adsorbed; when the desorption process needs to use the acidic desorption solution, the lithium hydroxide is prepared by the bipolar membrane, and the byproduct acid solution is used for desorbing the re-adsorbent, so that a closed cycle of the front and back processes is formed, and the additional raw material cost is saved; in addition, the crystallization mother liquor can be recycled, and the lithium yield is higher.
Drawings
FIG. 1 is a flow diagram of a process for extracting lithium hydroxide from carbonate-type salt lake brine.
Fig. 2 is a diagram of the device of the present invention.
Fig. 3 is a block diagram of a ceramic membrane module used in the present patent.
Wherein, 1, a prefilter; 2. an adsorption device; 3. a desorption liquid feeding tube; 4. a membrane concentration device; 5. purifying the resin column; 6. a bipolar membrane device; 7. an evaporative crystallizer; 8. a ceramic membrane module; 9. sealing the end; 10. a material inlet; 11. a material outlet; 12. a permeate outlet; 13. a ceramic membrane tube; 14. a joint at the inlet of the membrane tube; 15. the inner wall is a spiral groove.
Detailed Description
The salt lake brine to be treated by the utility model is mainly carbonate type brine, which contains more carbonate ions except lithium, magnesium, sodium and other ions.
The processing steps of the utility model are as follows:
step 1, pretreating salt lake brine; the purpose of this step is to carry out preliminary prefiltering to salt lake brine, can get rid of suspended particles etc. in the brine.
Step 2, adsorbing the brine obtained in the step 1 by using a lithium adsorbent, and desorbing the adsorbent by using a desorbent to obtain a desorption solution; the purpose of this step is to adsorb lithium in brine first, and after desorption, can reduce the ratio of sodium to lithium remarkably, and can remove most other ions, make the desorption liquid more suitable for the subsequent purification process of lithium.
Step 4, removing calcium and magnesium ions from the concentrated solution obtained in the step 3 by using purified resin to obtain a purified lithium-rich solution; because a certain amount of impurity ions such as calcium and magnesium still remain in the adsorption and desorption step, the aim of the step is to remove other calcium and magnesium ions in the brine.
Step 5, performing bipolar membrane electrolysis treatment on the purified lithium-rich solution obtained in the step 4 to obtain an acid solution and an alkali solution; in the step, through bipolar membrane electrolysis treatment, acid can be generated in an acid chamber of the electrolytic cell, and lithium hydroxide can be generated in a base chamber, so that the direct obtaining of lithium hydroxide through the steps is realized.
And 6, crystallizing the alkali solution obtained in the step 5 to obtain the lithium hydroxide.
In one embodiment, the pretreatment in step 1 is to filter off suspended matter.
In one embodiment, filtering out the suspended matter means filtering with a medium filter or a membrane filter.
In one embodiment, the membrane filter is a microfiltration membrane or an ultrafiltration membrane;
in one embodiment, the membrane filter is a hollow fiber, tubular or multi-channel membrane element.
In one embodiment, in the step 2, at least one of a titanium-based adsorbent and a manganese-based adsorbent is adsorbed.
In one embodiment, in the step 2, the desorption solution is an acid solution, wherein the hydrogen ion concentration is 0.01-1 mol/L.
In one embodiment, in step 2, the acid solution is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
In one embodiment, in the step 2, the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 0.5-5.0 g/L, 0.1-5.0 g/L, 0-0.05 g/L and 0-0.05 g/L respectively; the pH value of the desorption liquid is 1-7, and preferably 3-7.
In one embodiment, in step 3, the concentration is performed by membrane concentration; one or more of reverse osmosis, forward osmosis and electrodialysis can be adopted.
In one embodiment, in the step 3, the concentration of lithium ions, sodium ions, calcium ions and magnesium ions in the obtained concentrated solution is 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.8 g/L and 0-0.8 g/L respectively.
In one embodiment, in the step 4, the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the purified lithium-rich solution are respectively 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.005 g/L and 0-0.005 g/L.
In one embodiment, in the step 5, the concentration of hydrogen ions in the acid solution is 1.0 to 2.5 mol/L; the concentration of lithium ions in the alkali solution is 1.0-2.5 mol/L.
In one exemplary embodiment, the above process operates as follows:
(1) feeding salt lake brine into a pretreatment device to obtain pretreated brine;
(2) passing the pretreated brine through an adsorption device filled with a lithium adsorbent, eluting with a desorbent after adsorption is finished, and collecting desorption liquid;
(3) concentrating the obtained desorption solution by a membrane concentration system to obtain a concentrated solution;
(4) removing calcium and magnesium ions from the concentrated solution through a purification resin system to obtain a purified lithium-rich solution;
(5) sending the purified lithium-rich solution into a bipolar membrane system to obtain an acid solution and an alkali solution;
(6) and evaporating and crystallizing the alkali solution to obtain crystallization mother liquor and lithium hydroxide.
The method is characterized in that the salt lake brine in the step (1) is carbonate type salt lake brine; the pretreatment device is one or two combinations of a filter screen, a grating, a plate frame, a medium filter or a membrane filter.
The method is characterized in that the adsorbent in the step (2) is at least one of a titanium adsorbent or a manganese adsorbent; the desorbent is an acid solution with a certain concentration, and the concentration of hydrogen ions is 0.01-1 mol/L; the acid solution can be at least one of hydrochloric acid, sulfuric acid, nitric acid or acetic acid solution; the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 0.5-5.0 g/L, 0.1-5.0 g/L, 0-0.05 g/L and 0-0.05 g/L respectively; the pH value of the desorption solution is 1-7, and preferably 3-7.
The method described above, wherein the membrane concentration system in step (3) may be one or more of reverse osmosis, forward osmosis, electrodialysis and DTRO; the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the concentrated solution are respectively 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.8 g/L and 0-0.8 g/L.
The method is characterized in that the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the purified lithium-rich solution in the step (4) are respectively 2.0-20.0 g/L, 1.2-20.0 g/L, 0-0.005 g/L and 0-0.005 g/L.
The method is characterized in that the concentration of hydrogen ions in the acid solution in the step (5) is 1.0-2.5 mol/L; the concentration of lithium ions in the alkali solution is 1.0-2.5 mol/L.
Based on the above method, the device adopted by the utility model is shown in fig. 2, and comprises:
the pre-filter 1 is used for pre-filtering brine;
the adsorption device 2 is connected with the prefilter 1 and is used for carrying out lithium ion adsorption treatment on the water produced by the prefilter 1;
the membrane concentration device 4 is connected to the adsorption device 2 and is used for concentrating desorption liquid obtained in the adsorption device 2;
a purification resin column 5 connected to the concentration side of the membrane concentration device 4 for performing ion exchange calcium and magnesium removal treatment on the concentrated solution obtained in the membrane concentration device 4;
the bipolar membrane device 6 is connected with the purification resin column 5 and is used for electrolyzing the purified lithium-rich solution obtained from the purification resin column 5;
and the evaporative crystallizer 7 is connected with the alkali chamber of the bipolar membrane device 6 and is used for carrying out concentration and crystallization treatment on the solution containing the lithium hydroxide obtained in the alkali chamber.
In one embodiment, the pre-filter 1 is a screen, a grid, a plate frame, a media filter or a membrane filter.
In one embodiment, the membrane filter is provided with a hollow fiber type, tubular type or multi-channel type membrane element.
In one embodiment, the membrane filter is a microfiltration or ultrafiltration membrane.
In the process of pre-filtering salt lake brine, a cross-flow filtering mode is generally adopted, as shown in fig. 3, a tubular or multi-channel ceramic membrane adopted can form a filter cake of suspended matters in an internal channel, the thickness of the filter cake is different between a feed liquid inlet and a feed liquid outlet, the filter cake at the inlet of the feed liquid is easy to flush due to high flow velocity, so that the thickness of the filter cake at the inlet is small, the flow rate is reduced along with the permeation of the feed liquid near the outlet, the flushing force is weakened, and the thickness of the filter cake at the outlet is large; because the filter cake at the inlet is small in thickness, the surface of the ceramic membrane is easily exposed under the impact of suspended matters in the feed liquid, so that the scraping condition of the suspended matters on the surface of the ceramic membrane at the inlet of the feed liquid is easier to appear. Therefore, the structure of the tubular ceramic membrane or the multi-channel ceramic membrane adopted in the utility model is shown in fig. 3, the two ends of the ceramic membrane component 8 are provided with the end sockets 9, the end sockets 9 are respectively provided with the material inlet 10 and the material outlet 11, and the ceramic membrane component 8 is also provided with the penetrating fluid outlet 12; a ceramic membrane tube 13 is arranged in the ceramic membrane module 8, a conical membrane tube inlet joint 14 is arranged at one end, facing the material inlet 10, of the ceramic membrane tube 13, one side of a conical larger cross section faces the material inlet 10, and an inner wall spiral groove 15 is formed in the wall surface of the inner portion of the membrane tube inlet joint 14. By adopting the structure, when salt lake salt water flows in from the material inlet 10, the salt lake salt water firstly enters the conical membrane tube inlet joint 14, liquid can generate rotational flow due to the spiral groove in the salt lake salt water, suspended matters are concentrated in the middle of the inlet material, a large amount of suspended matters can not directly contact with the wall surface at the inlet end of the ceramic membrane tube 13, when the rotational flow effect gradually disappears, the material flows to the position near the outlet end of the ceramic membrane tube 14, a thicker filter cake layer is arranged in the region, and the condition of membrane surface abrasion caused by direct friction with the wall surface can not be generated.
In one embodiment, the adsorption device 2 is loaded with an adsorbent for adsorbing lithium ions.
In one embodiment, the lithium adsorbent is at least one of a titanium-based adsorbent or a manganese-based adsorbent.
In one embodiment, a desorption liquid feeding pipe 3 is disposed on the adsorption device 2 for feeding desorption liquid into the adsorption device 2.
In one embodiment, the membrane concentration device 4 is one or more of a reverse osmosis membrane system, a forward osmosis membrane system, a DTRO membrane system, or an electrodialysis system.
Example 1
This embodiment provides a method for preparing lithium hydroxide from a carbonate-type salt lake, where the brine used is a carbonate-type brine, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions, and chloride ions in the brine are 1.2g/L, 100g/L, 0.1g/L, 0.5g/L, 35g/L, and 120g/L, respectively, and the method of this embodiment includes the following steps:
and (3) feeding the carbonate brine into an ultrafiltration system to remove part of mechanical impurities such as silt and the like to obtain the brine after impurity removal.
Feeding the pretreated brine into an adsorption device filled with a titanium adsorbent, desorbing by using 0.3mol/L hydrochloric acid solution after adsorption is finished to obtain desorption solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are respectively 2g/L, 1.2g/L, 0.01g/L and 0.01g/L, and the pH value of the desorption solution is 5.3.
And (3) feeding the desorption solution into a first-stage reverse osmosis system, wherein the reverse osmosis operation pressure is 2.0 MPa, the concentration of lithium ions in the desorption solution is concentrated by 2 times to obtain first-stage reverse osmosis concentrated water and first-stage reverse osmosis fresh water, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis system to be concentrated by 20 times and is mixed with the first-stage reverse osmosis concentrated solution, and the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the obtained reverse osmosis concentrated solution are respectively 4.0g/L, 2.4g/L, 0.02g/L and 0.02 g/L.
And concentrating the reverse osmosis concentrated solution by an electrodialysis system, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the electrodialysis concentrated water are respectively 16g/L, 9.6g/L, 0.1g/L and 0.1 g/L.
And introducing the electrodialysis concentrated solution into a purification resin device to obtain a purified lithium-rich solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the lithium-rich solution are respectively 16g/L, 9.6g/L, 0.001g/L and 0.001 g/L.
And introducing the purified lithium-rich solution into a bipolar membrane system, wherein the concentration of hydrogen ions in an acid solution obtained in an acid chamber of the bipolar membrane is 2mol/L, the concentration of lithium ions in an alkali solution obtained in an alkali chamber is 1.5mol/L, and the concentration of lithium ions in fresh brine generated by the bipolar membrane is 4.2 g/L.
And crystallizing the alkali liquor generated by the bipolar membrane, and washing and drying the product to obtain the lithium hydroxide.
Example 2
This embodiment provides a method for preparing lithium hydroxide from a carbonate-type salt lake, in which the brine is a carbonate-type brine, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions, and chloride ions in the brine are 1.0g/L, 90g/L, 0.08g/L, 0.3g/L, 32g/L, and 105g/L, respectively, and the method of this embodiment includes the following steps:
and (3) feeding the carbonate brine into a multi-media filter to remove part of mechanical impurities such as silt and the like, so as to obtain the brine after impurity removal.
Feeding the pretreated brine into an adsorption device filled with a titanium adsorbent, desorbing by using 0.3mol/L hydrochloric acid solution after adsorption is finished to obtain desorption solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 1.9g/L, 1.1g/L, 0.01g/L and 0.01g/L respectively, and the pH value of the desorption solution is 6.2.
And (3) feeding the desorption solution into a first-stage reverse osmosis system, wherein the reverse osmosis operation pressure is 2.5MPa, the concentration of lithium ions in the desorption solution is concentrated by 2.4 times to obtain first-stage reverse osmosis concentrated water and first-stage reverse osmosis fresh water, the first-stage reverse osmosis fresh water is fed into a second-stage reverse osmosis system to be concentrated by 24 times and is mixed with the first-stage reverse osmosis concentrated solution, and the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the obtained reverse osmosis concentrated solution are respectively 4.3g/L, 2.6g/L, 0.03g/L and 0.03 g/L.
And concentrating the reverse osmosis concentrated solution by an electrodialysis system, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the electrodialysis concentrated water are respectively 17g/L, 10.4g/L, 0.12g/L and 0.13 g/L.
And introducing the electrodialysis concentrated solution into a purification resin device to obtain a purified lithium-rich solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the lithium-rich solution are 17g/L, 10.3g/L, 0.001g/L and 0.001g/L respectively.
And introducing the purified lithium-rich solution into a bipolar membrane system, wherein the concentration of hydrogen ions in an acid solution obtained in an acid chamber of the bipolar membrane is 2.2mol/L, the concentration of lithium ions in an alkali solution obtained in an alkali chamber is 1.6mol/L, and the concentration of lithium ions in fresh brine generated by the bipolar membrane is 4.4 g/L.
And crystallizing the alkali liquor generated by the bipolar membrane, and washing and drying the product to obtain the lithium hydroxide.
Example 3
This embodiment provides a method for preparing lithium hydroxide from a carbonate-type salt lake, where the brine used is a carbonate-type brine, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions, and chloride ions in the brine are 1.2g/L, 100g/L, 0.1g/L, 0.5g/L, 35g/L, and 120g/L, respectively, and the method of this embodiment includes the following steps:
and (3) feeding the carbonate brine into a plate-and-frame filter to remove part of mechanical impurities such as silt and the like, so as to obtain the brine after impurity removal.
Feeding the pretreated brine into an adsorption device filled with a titanium adsorbent, desorbing by using 0.4mol/L hydrochloric acid solution after adsorption is finished to obtain desorption solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are respectively 2.3g/L, 1.3g/L, 0.02g/L and 0.03g/L, and the pH value of the desorption solution is 3.1.
And (3) feeding the desorption solution into a first-stage reverse osmosis system, wherein the reverse osmosis operation pressure is 1.8 MPa, the concentration of lithium ions in the desorption solution is concentrated by 2 times to obtain first-stage reverse osmosis concentrated water and first-stage reverse osmosis fresh water, the first-stage reverse osmosis fresh water enters a second-stage reverse osmosis system to be concentrated by 20 times and is mixed with the first-stage reverse osmosis concentrated solution, and the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the obtained reverse osmosis concentrated solution are respectively 3.7g/L, 2.3g/L, 0.01g/L and 0.02 g/L.
And concentrating the reverse osmosis concentrated solution by an electrodialysis system, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the electrodialysis concentrated water are respectively 15g/L, 9.3g/L, 0.08g/L and 0.1 g/L.
And introducing the electrodialysis concentrated solution into a purification resin device to obtain a purified lithium-rich solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the lithium-rich solution are respectively 15.5g/L, 9.3g/L, 0.001g/L and 0.001 g/L.
And introducing the purified lithium-rich solution into a bipolar membrane system, wherein the concentration of hydrogen ions in an acid solution obtained in an acid chamber of the bipolar membrane is 1.9mol/L, the concentration of lithium ions in an alkali solution obtained in an alkali chamber is 1.4mol/L, and the concentration of lithium ions in fresh brine generated by the bipolar membrane is 4.0 g/L.
And crystallizing the alkali liquor generated by the bipolar membrane, and washing and drying the product to obtain the lithium hydroxide.
Example 4
This embodiment provides a method for preparing lithium hydroxide from a carbonate-type salt lake, where the brine used is a carbonate-type brine, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions, and chloride ions in the brine are 0.8g/L, 90g/L, 0.1g/L, 0.5g/L, 28g/L, and 115g/L, respectively, and the method of this embodiment includes the following steps:
feeding the pretreated brine into an adsorption device filled with a manganese adsorbent, desorbing the pretreated brine by using 0.4mol/L hydrochloric acid solution after adsorption is finished to obtain desorption solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 1.9g/L, 0.8g/L, 0.01g/L and 0.08g/L respectively, and the pH value of the desorption solution is 4.5.
And (3) feeding the desorption solution into a reverse osmosis system, wherein the reverse osmosis operation pressure is 8MPa, and the concentration of lithium ions in the desorption solution is concentrated by 5 times to obtain reverse osmosis concentrated solution with the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions of 9g/L, 3.8g/L, 0.045g/L and 0.4g/L respectively.
And introducing the reverse osmosis concentrated solution into a purification resin device to obtain a purified lithium-rich solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the lithium-rich solution are respectively 9g/L, 3.8g/L, 0.001g/L and 0.002 g/L.
And introducing the purified lithium-rich solution into a bipolar membrane system, wherein the concentration of hydrogen ions in an acid solution obtained in an acid chamber of the bipolar membrane is 1.1mol/L, the concentration of lithium ions in an alkali solution obtained in an alkali chamber is 1.0mol/L, and the concentration of lithium ions in fresh brine generated by the bipolar membrane is 2.3 g/L.
And crystallizing the alkali liquor generated by the bipolar membrane, and washing and drying the product to obtain the lithium hydroxide.
Example 5
This embodiment provides a method for preparing lithium hydroxide from a carbonate-type salt lake, where the brine used is a carbonate-type brine, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements, carbonate ions, and chloride ions in the brine are 0.8g/L, 90g/L, 0.1g/L, 0.5g/L, 28g/L, and 115g/L, respectively, and the method of this embodiment includes the following steps:
feeding the pretreated brine into an adsorption device filled with a manganese adsorbent, desorbing the pretreated brine by using 0.4mol/L hydrochloric acid solution after adsorption is finished to obtain desorption solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the desorption solution are 1.9g/L, 0.8g/L, 0.01g/L and 0.08g/L respectively, and the pH value of the desorption solution is 6.5.
And (2) feeding the desorption solution into a forward osmosis system, wherein salt lake old brine is adopted as a drawing solution in the forward osmosis system (the NaCl concentration is about 90 g/L), the flow rate of a feeding solution is about 4.5cm/s, the flow rate of the drawing solution is about 0.5cm/s, and the concentration of lithium ions, sodium ions, calcium ions and magnesium ions in the forward osmosis concentrated solution is about 2 times that of the forward osmosis concentrated solution after the forward osmosis is finished, so that the concentrations of the lithium ions, the sodium ions, the calcium ions and the magnesium ions in the forward osmosis concentrated solution are respectively 4.1g/L, 1.5g/L, 0.02g/L and 0.14 g.
And introducing the reverse osmosis concentrated solution into a purification resin device to obtain a purified lithium-rich solution, wherein the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the lithium-rich solution are respectively 4.1g/L, 1.5g/L, 0.001g/L and 0.001 g/L.
And introducing the purified lithium-rich solution into a bipolar membrane system, wherein the concentration of hydrogen ions in an acid solution obtained in an acid chamber of the bipolar membrane is 0.8mol/L, the concentration of lithium ions in an alkali solution obtained in an alkali chamber is 0.7mol/L, and the concentration of lithium ions in fresh brine generated by the bipolar membrane is 1.5 g/L.
And crystallizing the alkali liquor generated by the bipolar membrane, and washing and drying the product to obtain the lithium hydroxide.
Example 6
The difference between the example and the example 5 is that the desorption solution is sent to a DTRO membrane system, the operation pressure is 10MPa, the concentration of lithium ions in the desorption solution is concentrated by 8 times, and the concentrations of lithium ions, sodium ions, calcium ions and magnesium ions in the DTRO membrane concentrated solution are 15.2g/L, 6.4g/L, 0.08g/L and 0.64g/L respectively.
Other conditions were exactly the same as in example 5.
Claims (10)
1. A device for extracting lithium from a salt lake is characterized by comprising:
the membrane concentration device (4) is connected to the adsorption device (2) and is used for concentrating desorption liquid obtained in the adsorption device (2);
a purification resin column (5) connected to the concentration side of the membrane concentration device (4) and used for removing calcium and magnesium from the concentrated solution obtained in the membrane concentration device (4);
the bipolar membrane device (6) is connected with the purification resin column (5) and is used for electrolyzing the purified lithium-rich solution obtained in the purification resin column (5);
and the evaporative crystallizer (7) is connected with the alkali chamber of the bipolar membrane device (6) and is used for carrying out concentration crystallization treatment on the solution containing the lithium hydroxide obtained in the alkali chamber.
2. The device for extracting lithium from a salt lake according to claim 1, further comprising: the pre-filter (1) is used for pre-filtering brine, and the adsorption device (2) is connected to the pre-filter (1).
3. The device for extracting lithium from salt lake according to claim 2, wherein the pre-filter (1) is a filter screen, a grid, a plate frame, a medium filter or a membrane filter.
4. The device for extracting lithium from salt lake as claimed in claim 3, wherein the membrane filter is provided with hollow fiber type, tubular type or multi-channel type membrane elements; the membrane filter is a microfiltration membrane or an ultrafiltration membrane.
5. The device for extracting lithium from salt lake according to claim 4, wherein the structure of the membrane filter comprises a ceramic membrane component (8), two ends of the ceramic membrane component (8) are provided with end sockets (9), the end sockets (9) are respectively provided with a material inlet (10) and a material outlet (11), and the ceramic membrane component (8) is further provided with a penetrating fluid outlet (12); the ceramic membrane module is characterized in that a ceramic membrane tube (13) is arranged in the ceramic membrane module (8), a conical membrane tube inlet joint (14) is arranged at one end, facing the material inlet (10), of the ceramic membrane tube (13), one side of a conical larger section faces the material inlet (10), and an inner wall spiral groove (15) is formed in the wall surface of the inner portion of the membrane tube inlet joint (14).
6. The device for extracting lithium from salt lake as claimed in claim 1, wherein the adsorption device (2) is filled with an adsorbent for adsorbing lithium ions.
7. The device for extracting lithium from the salt lake according to claim 6, wherein the adsorbent is a titanium adsorbent or a manganese adsorbent.
8. The device for extracting lithium from salt lake according to claim 1, wherein the adsorption device (2) is provided with a desorption liquid feeding pipe (3) for feeding desorption liquid into the adsorption device (2).
9. The device for extracting lithium from a salt lake according to claim 1, further comprising: and the acid adjusting tank is used for adjusting the pH of the acid solution obtained in the bipolar membrane device (6) and desorbing the acid solution in the adsorption device (2).
10. The device for extracting lithium from salt lake according to claim 1, wherein the membrane concentration device (4) is one or more of a reverse osmosis membrane, a forward osmosis membrane, an electrodialysis membrane and a DTRO membrane.
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