CN219279499U - Lithium extraction device for salt lake brine - Google Patents
Lithium extraction device for salt lake brine Download PDFInfo
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Abstract
The utility model relates to a device for extracting lithium from salt lake brine, which comprises: an adsorbent tank for adsorbing lithium to brine; the salt concentration device is connected with the adsorbent tank and used for concentrating eluent in the adsorbent tank; the reactor is connected to the concentration side of the salt concentration device and is used for carrying out lithium precipitation reaction on the concentrated feed liquid; a phosphate adding tank and an alkali liquor adding tank which are respectively connected with the reactor and are used for adding phosphate and alkali into the reactor; and the solid-liquid separation device is connected with the reactor and is used for carrying out solid-liquid separation on the generated precipitate. The method has high lithium yield in the preparation process, and is simple, and the obtained lithium phosphate can be used for preparing the battery material lithium iron phosphate.
Description
Technical Field
The utility model relates to the field of lithium extraction in salt lakes, in particular to a device for extracting lithium from salt lake brine in high yield.
Background
Lithium and its compounds are widely used in various fields such as batteries, medicine, aerospace, chemical industry and national defense due to their excellent properties, and occupy a vital role in economic development, and are known as "21 st century new energy". The lithium resource is mainly from lithium ore and salt lake brine, and the content of lithium in the salt lake brine is highest, and the lithium resource accounts for 66% of world lithium reserves. China is a large country of lithium resources, and reserves are in the first place of the world. Wherein, the lithium resource reserves of the salt lakes of Qinghai and Tibet account for more than 85 percent of the total reserves of China.
The process for extracting lithium from the salt lake brine is simple, low in cost and environment-friendly, meets market demands, and at present, the research object for extracting lithium is mainly the salt lake brine. In the prior art, however, most of the lithium-rich solution is obtained from salt lake brine, and then CO is introduced into the salt lake brine by using sodium carbonate solution or alkaline environment 2 Precipitating lithium to obtain a lithium carbonate product. The lithium concentration in the lithium deposition mother solution of the lithium deposition technology is more than 1g/L, and the lithium loss in the lithium deposition process is more than 15%. CN109019642a discloses a method for extracting lithium carbonate from salt lake brine, the recovery rate of the utility model for lithium carbonate is lower, which is between 40 and 52%. CN104828846a discloses a method for purifying and separating lithium carbonate mixed salt by using high-temperature brine, the yield of the lithium carbonate produced by the utility model is also lower, which is about 50%.
CN110357055a discloses a method for extracting lithium from salt lake brine and preparing lithium phosphate and application thereof, and the extraction rate of the method for extracting lithium from salt lake brine is more than 94%. However, said utility model is limited by the grade of brine, only suitable for brine with lithium concentration of 2-5 g/L, and said brine is characterized by that the underground brine is placed in salt field and dried for more than 3 years, and its period is long; the oxalic acid is used for removing calcium, magnesium and other ions in the brine, so that a large amount of medicines are consumed, the environment is not protected, and a large amount of generated precipitate can entrain lithium ions, so that excessive lithium loss is caused.
Therefore, the development of the high-yield environment-friendly salt lake lithium extraction technology which is not limited by the type and grade of brine has important significance for the new energy field.
Disclosure of Invention
The utility model aims to provide a method for extracting lithium from salt lake brine with high yield, which comprises the steps of adsorbing lithium in the salt lake brine by using a lithium-extracting adsorbent, leaching and desorbing to obtain a lithium-containing desorption liquid, and concentrating the lithium-containing desorption liquid to obtain a lithium-containing concentrated solution; the lithium phosphate can be prepared by adding a phosphate group-containing medicament to the lithium-containing desorption solution or the concentrated solution and controlling the reaction temperature and the pH value.
A method for extracting lithium from salt lake brine comprises the following steps:
step 1, adsorbing lithium from brine through an adsorbent, and eluting to obtain an eluent containing lithium;
and 2, adding phosphate into the eluent containing lithium to perform precipitation reaction of lithium, and separating the obtained precipitate to obtain lithium phosphate.
In the step 1, the concentration of lithium in brine is 0.02-5.0 g/L, and the adsorbent is at least one of an aluminum salt adsorbent, a titanium adsorbent or a manganese adsorbent; the concentration of lithium in the lithium-containing eluent is 0.4-12.0 g/L.
In the step 1, chloride type salt lake brine, magnesium sulfate subtype salt lake brine, carbonate type salt lake brine, deep underground brine and the like are taken as raw materials.
In the step 2, the lithium concentration in the lithium-containing eluent is 0.4-12.0 g/L; when the concentration of lithium in the lithium-containing eluent is 0.4-1.5 g/L, the eluent is further concentrated and then sent into precipitation reaction.
The concentration treatment is one or a combination of a plurality of reverse osmosis membrane, forward osmosis membrane, electrodialysis and evaporation treatment.
The phosphate solution can be one or more of phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium hydrogen phosphate, monoammonium phosphate and ammonium phosphate.
The phosphate usage is calculated according to the mole ratio of phosphate radical to lithium ion of 1:3, and the phosphate radical can be excessive by 3-15 wt%.
The pH in the precipitation reaction can be controlled to 9.0 or more, preferably 10.0 to 14.0.
The pH value is realized by adding one or a combination of more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia water, ammonium carbonate and ammonium bicarbonate.
The precipitate is separated by centrifugation, sedimentation or filtration, and the precipitate obtained by separation is dried.
The filtering mode is that ceramic membrane filtration is carried out firstly, then plate-frame filtration is carried out on ceramic membrane concentrated solution, and the aperture of the ceramic membrane is 10-500nm; and after the ceramic membrane is filtered, the acid liquor is adopted to carry out cross-flow cleaning on the surface, and the cross-flow speed is 1-10m/s.
The time of cross-flow cleaning is calculated by the following steps:
step S1, obtaining particle diameter differential distribution data of ferric phosphate obtained under different reaction conditions, and obtaining pore diameter differential distribution data of different ceramic membranes;
step S2, concentrating precipitated iron phosphate suspension with different particle size distribution data through ceramic membranes with different pore size distribution data, wherein the concentration process is carried out under different cross-flow velocity conditions; after the concentration is finished, the ceramic membrane is washed and cleaned by adopting different cross-flow cleaning time, and the flux recovery rate under different cleaning time periods is calculated;
step S3, traversing the particle size value on the particle size differential distribution data for each set of experimental results performed in step S2, and obtaining a particle size value d smaller than the current particle size value per traversal pi Is the curve integral area S of (2) pi (i= … … n) while obtaining a pore diameter larger than d on the pore diameter differential distribution data di Is the curve integral area S of (2) di Wherein d is di ＝d pi +δ, δ is a parameter; sum of calculated areas S i ＝S pi +S di After all traversals are completed, the sum of areas S is obtained i Maximum S in vector max ；
S4, fitting the following formula according to the data obtained in the step S3,
wherein N refers to the recovery rate of membrane flux, t is cross-flow cleaning time, and a and b are parameters;
s5, performing new ceramic membrane concentration treatment of ferric phosphate precipitation, taking N' =alpha×N as a target recovery rate of a membrane cleaning process, wherein alpha is a parameter, and substituting the parameter into the formula (1) to calculate the optimal cleaning time.
Alpha is 0.9-0.95, delta is 30-50nm.
A salt lake brine lithium extraction device, comprising:
an adsorbent tank for adsorbing lithium to brine;
the salt concentration device is connected with the adsorbent tank and used for concentrating eluent in the adsorbent tank;
the reactor is connected to the concentration side of the salt concentration device and is used for carrying out lithium precipitation reaction on the concentrated feed liquid;
a phosphate adding tank and an alkali liquor adding tank which are respectively connected with the reactor and are used for adding phosphate and alkali into the reactor;
and the solid-liquid separation device is connected with the reactor and is used for carrying out solid-liquid separation on the generated precipitate.
The solid-liquid separation device is one or the combination of a plurality of centrifuges, settling tanks and filters.
The solid-liquid separation device comprises a ceramic membrane and a plate-frame filter which are sequentially connected.
Further comprises: and the dryer is connected with the solid-liquid separation device and is used for drying the separated solid.
Further comprises: the eluent is added into the tank and connected with the adsorbent tank for eluting the adsorbent.
The salt concentration device is one or a combination of more of a reverse osmosis membrane, a forward osmosis membrane, electrodialysis and an evaporation device.
The average pore diameter of the ceramic membrane ranges from 20nm to 500nm.
Advantageous effects
Compared with the prior art, the utility model has the following beneficial effects:
(1) The utility model has wider application range, is hardly limited by the type and grade of brine, and can be applied to the brine taking chloride type salt lake brine, magnesium sulfate subtype salt lake brine, carbonate type salt lake brine, deep underground brine and the like with the lithium concentration of 0.02-5.0 g/L as raw materials, and can be directly extracted from underground or ground surface or can be evaporated and concentrated to separate out salt.
(2) In the lithium deposition process, the recovery rate of lithium is high and is 93.0-99.5%.
(3) The preparation process is simple to operate, low in cost, free from consumption of a large amount of chemicals and free from environmental hazards.
Drawings
Fig. 1 is a flow chart of a method for extracting lithium from salt lake brine in high yield.
Fig. 2 is a diagram of a lithium extraction device.
The left half of fig. 3 is the particle size distribution of the particles, and the right half is the pore size distribution of the ceramic membrane.
Fig. 4 is a comparison of calculated and predicted values.
FIG. 5 is a film cleaning result.
Wherein, 1, an adsorbent tank; 2. adding eluent into the tank; 3. a salt concentration device; 4. a reactor; 5. adding phosphate into the tank; 6. adding alkali liquor into the tank; 7. a solid-liquid separation device; 8. a ceramic membrane; 9. a plate frame filter; a dryer.
Detailed Description
The utility model aims to extract lithium from lithium-containing brine, and the lithium-containing brine is used as a treatment raw material, and can be chloride type salt lake brine, magnesium sulfate subtype salt lake brine, carbonate type salt lake brine, deep underground brine and the like, wherein the brine can be directly extracted from underground or ground surface, or can be the brine subjected to evaporation concentration to separate out salt, and the lithium concentration in the salt lake brine is 0.02-5.0 g/L.
To achieve the above object, the steps of the present utility model are described in detail as follows:
step (1), delivering salt lake brine into a device filled with a lithium extraction adsorbent for adsorption, eluting and desorbing the lithium extraction adsorbent after the adsorption is finished, and collecting lithium-containing desorption liquid;
step (2), delivering the lithium-containing desorption solution into a concentrating device for concentrating to obtain a lithium-containing concentrated solution;
and (3) delivering the lithium-containing desorption solution or the lithium-containing concentrated solution into a lithium precipitation device, adding a phosphate-containing solution, controlling the reaction pH value and the reaction temperature, and collecting a reaction precipitate, namely lithium phosphate.
In step (1), the lithium extraction adsorbent may be optionally at least one of an aluminum salt adsorbent, a titanium-based adsorbent, or a manganese-based adsorbent.
Optionally, the lithium concentration in the lithium-containing desorption liquid is 0.4-12.0 g/L; wherein, the lithium desorption liquid with the lithium concentration of 0.4-1.5 g/L is sent into a concentration device; the desorption liquid containing lithium with the concentration of 1.5-12.0 g/L can be sent into a concentration device or directly into a lithium precipitation device.
In step (2), the concentrating device may be one or more of a reverse osmosis membrane, a forward osmosis membrane, electrodialysis, and an evaporating device.
Optionally, the lithium concentration in the lithium-containing concentrate is 1.5-20.0 g/L.
Alternatively, the phosphate-containing solution may be one or more of phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium phosphate.
Wherein the concentration of the phosphate-containing solution is 15-50 wt%.
Further preferably, the phosphate-containing solution has a concentration of 25 to 40wt%.
Wherein the dosage of the phosphate-containing solution is calculated according to the mole ratio of phosphate radical to lithium ion of 1:3, and the phosphate radical can be excessive by 3-15 wt%.
Further preferably, the phosphate may be in excess of 5 to 10wt%.
Alternatively, the pH may be controlled to 9.0 or higher.
Further preferably, the pH value can be controlled to 10.0 to 14.0.
Optionally, the pH control is achieved by adding one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia, ammonium carbonate, ammonium bicarbonate.
Optionally, the reaction temperature is controlled between 30 and 100 ℃.
Further preferably, the reaction temperature is controlled to 60 to 90 ℃.
Optionally, the lithium yield in the lithium precipitation process is 93.0-99.5%.
Alternatively, in the step (3), the reaction precipitate may be collected by centrifugation, sedimentation separation, membrane separation, or the like, preferably by using a ceramic membrane, and the concentrated solution of the ceramic membrane may be filtered by a plate frame to obtain a wet material. The purity of the lithium phosphate is not lower than 90% after drying.
Further preferably, after the ceramic membrane is concentrated, the surface of the ceramic membrane channel is subjected to cross-flow cleaning by adopting acid liquor so as to recover the membrane flux.
Further preferably, the time for optimal cleaning of the ceramic membrane by cross-flow is calculated by the following steps:
step S1, obtaining particle diameter differential distribution data of ferric phosphate obtained under different reaction conditions, and obtaining pore diameter differential distribution data of different ceramic membranes; the particle size distribution data can be obtained by detecting the suspension after precipitation reaction by a laser particle size analyzer, and precipitation with a certain difference of particle size distribution is obtained under different reaction conditions for the precipitation process of ferric phosphate, and most particles usually have the particle size of 30-50nm, but some too small particles, such as precipitation particles of 10-15nm, are also formed; the pore size distribution of the ceramic membrane can be detected by a bubble pressure method, and the ceramic membrane is generally characterized by narrow pore size distribution, but larger membrane pores still exist, for example, for a ceramic membrane with an average pore size of 50nm, the surface of the ceramic membrane is generally provided with large pores of 100nm or even a small number of 150 nm; the small-particle-size precipitated particles can cause blocking of the membrane pores if the small-particle-size precipitated particles are permeated into the larger membrane pores, and in the process of cross-flow cleaning of the membrane, the blocked particles are not easy to be carried away by scouring of the surface of the membrane, and only a certain outward permeation can be generated in the pores through scouring of the surface of the membrane for a longer time so as to be slowly carried away from the membrane pores, so that the ceramic membrane with the blocking of the membrane pores is required to take more cleaning time;
step S2, concentrating precipitated iron phosphate suspension with different particle size distribution data through ceramic membranes with different pore size distribution data, wherein the concentration process is carried out under different cross-flow velocity conditions; after the concentration is finished, the ceramic membrane is washed and cleaned by adopting different cross-flow cleaning time, and the flux recovery rate under different cleaning time periods is calculated; the purpose of this step is to obtain initial accumulation data of the effect of cleaning the ceramic membrane in the case of different parameters of the precipitated particles, typically with a recovery rate of flux of percentage, but most of the time not reaching 100%, but approaching this value, for example around 90%.
Step S3, traversing the particle size value on the particle size differential distribution data for each set of experimental results performed in step S2, and obtaining a particle size value d smaller than the current particle size value per traversal pi Is the curve integral area S of (2) pi (i= … … n) while obtaining a pore diameter larger than d on the pore diameter differential distribution data di Is the curve integral area S of (2) di Wherein d is di ＝d pi +δ, δ is a parameter; sum of calculated areas S i ＝S pi +S di After all traversals are completed, the sum of areas S is obtained i Maximum S in vector max The method comprises the steps of carrying out a first treatment on the surface of the As shown in fig. 3, the particle size distribution of the particles is shown on the left side, and at the cut line (i.e., the point of the numerical value currently traversed), the integral area of the curve smaller than its particle size represents the ratio of particles smaller than this current particle size, and these smaller particles are more likely to plug the membrane pores, resulting in clogging of the membrane; while the pore size distribution of the ceramic membrane is shown on the right side of FIG. 3, the cut line represents d di Since the membrane pores are generally overlapped at the surface particles, and the membrane pores are not easily blocked by the accumulation of particles even if the membrane pores are slightly larger than the particle diameter of the particles, a certain margin (δ in the above formula) can be appropriately widened when evaluating the blocking of the membrane pores, and for example, when the current traversing particle diameter is 30nm, the ratio of large pores having a pore diameter of more than 50nm can be examined by taking δ=20nm. When each pass is taken, two integral areas can be obtained, representing the ratio of small particle size to large membrane pore, respectively, when the sum of the two integral areas is at a maximum, this means that the small particle size and the large membrane pore can be matched to each other to the maximum, which also represents the case that the small particle size which can be achieved under the current particle size/particle size distribution characteristics enters the larger membrane pore, which also represents the occurrence of a membrane when concentration is carried outThe proportion of the pores occupied by small particles is a parameter which affects the effectiveness of the membrane cleaning.
S4, fitting the following formula according to the data obtained in the step S3,
wherein N refers to the recovery rate of membrane flux, t is cross-flow cleaning time, and a and b are parameters; the magnitude of the proportion parameter in S3 is inversely proportional to the cleaning recovery rate of the membrane, and the cleaning recovery rate has a marginal effect on the cleaning time length, so that a relation between the recovery rate and the integral area and the cleaning time can be constructed.
S5, performing new ceramic membrane concentration treatment of ferric phosphate precipitation, taking N' =alpha×N as a target recovery rate of a membrane cleaning process, wherein alpha is a parameter, and substituting 0.9-0.95 into the formula to calculate the optimal cleaning time. In this step, since the recovery rate of 100% cannot be normally achieved when the film cleaning is performed, when α=0.9 to 0.9 is taken, it is considered that the set cleaning purpose is achieved, and the cleaning can be stopped, and the cleaning time at this time is the final estimated value.
Based on the above method, the device adopted by the patent is shown in fig. 2, and includes:
an adsorbent tank 1 for adsorbing lithium to brine;
a salt concentration device 3 connected to the adsorbent tank 1 for concentrating the eluent in the adsorbent tank 1;
a reactor 4 connected to the concentration side of the salt concentration device 3 for performing a lithium precipitation reaction on the concentrated feed solution;
a phosphate adding tank 5 and an alkali liquor adding tank 6, which are respectively connected to the reactor 4, for adding phosphate and alkali to the reactor 4;
a solid-liquid separation device 7 connected to the reactor 4 for separating solid from liquid in the produced precipitate.
The solid-liquid separation device 7 is one or a combination of a plurality of centrifuges, settling tanks and filters.
The solid-liquid separation device 7 comprises a ceramic membrane 8 and a plate-frame filter 9 which are sequentially connected.
Further comprises: and a dryer 10 connected to the solid-liquid separation device 7 for drying the separated solid.
Further comprises: the eluent is added into the tank 2 and connected with the adsorbent tank 1 for eluting the adsorbent.
The salt concentration device 3 is one or a combination of a plurality of reverse osmosis membrane, forward osmosis membrane, electrodialysis and evaporation device.
The average pore diameter of the ceramic membrane 8 is in the range of 20-500nm.
Example 1
The brine used in this embodiment is a chloride brine, and the concentrations of the main ions sodium ions, calcium ions, lithium ions, boron elements and chloride ions contained in the brine are 89.0g/L, 20.5g/L, 0.02g/L, 0.21g/L and 199.5g/L, respectively, and the flow of this embodiment is shown in fig. 1, and the method of this embodiment includes the following steps:
and (3) sending the brine into a device filled with an aluminum adsorbent for adsorption, and after the adsorption is finished, sequentially eluting and desorbing, and collecting a lithium-containing desorption solution, wherein the lithium concentration is 0.4g/L.
And (3) delivering the lithium-containing desorption solution into a reverse osmosis membrane device for concentration to obtain a lithium-containing concentrated solution, wherein the lithium concentration is 1.5g/L.
And (3) sending the lithium-containing concentrated solution into a lithium precipitation device, heating to 60 ℃, adding a phosphoric acid solution with the mass fraction of 25wt%, ensuring that the phosphate is excessive by 5wt%, regulating the pH value to 10.0 by using a sodium hydroxide solution, concentrating by using a 50um ceramic membrane, filtering by using a plate frame, washing by using hot water, and drying to obtain white powder, namely the lithium phosphate with the purity of 90.1%.
Wherein, the yield of lithium in the lithium precipitation process is 93.3%.
Example 2
In the embodiment, a certain magnesium sulfate subtype salt lake brine is adopted, wherein the concentrations of main ions including sodium ions, magnesium ions, lithium ions, boron elements, chloride ions and sulfate radicals are 91.0g/L, 30.9g/L, 0.3g/L, 0.35g/L, 190.4g/L and 25.1g/L respectively, and the specific operation steps are as follows:
and (3) sending the brine into a device filled with a manganese adsorbent for adsorption, and after the adsorption is finished, sequentially eluting and desorbing, and collecting a lithium-containing desorption solution, wherein the lithium concentration is 0.8g/L.
And (3) sequentially delivering the lithium-containing desorption solution into a reverse osmosis membrane, a forward osmosis membrane, an electrodialysis device and an evaporation device for concentration to obtain a lithium-containing concentrated solution, wherein the lithium concentration is 20.1g/L.
And (3) sending the lithium-containing concentrated solution into a lithium precipitation device, heating to 90 ℃, adding a disodium hydrogen phosphate solution with the mass fraction of 40wt% to ensure that the phosphate is excessive by 10wt%, regulating the pH value to be 14.0 by using a sodium carbonate solution, concentrating by using a 50um ceramic membrane, filtering by using a plate frame, washing by hot water, and drying to obtain white powder, namely the lithium phosphate with the purity of 98.3%.
Wherein, the yield of lithium in the lithium precipitation process is 99.5%.
Example 3
In the embodiment, a certain carbonate type salt lake brine is adopted, wherein the concentration of main ions including sodium ions, magnesium ions, lithium ions, boron elements, chloride ions, carbonate and bicarbonate is 39.0g/L, 1.3g/L, 0.15g/L, 0.75g/L, 58g/L, 2.1g/L and 1.4g/L respectively, and the specific operation steps are as follows:
and (3) sending the brine into a device filled with a titanium adsorbent for adsorption, and after the adsorption is finished, sequentially eluting and desorbing, and collecting a lithium-containing desorption solution, wherein the lithium concentration is 12.2g/L.
Directly sending the desorption solution containing lithium into a lithium precipitation device, heating to 80 ℃, adding a sodium dihydrogen phosphate solution with the mass fraction of 30wt%, ensuring that the phosphate radical is excessive by 8wt%, regulating the pH value to 12.0 by using a potassium hydroxide solution, concentrating by using a 50um ceramic membrane, filtering by using a plate frame, washing by using hot water, and drying to obtain white powder, namely the lithium phosphate with the purity of 98.5%.
Wherein, the yield of lithium in the lithium precipitation process is 99.2 percent.
Example 4
In the embodiment, a certain brine which is evaporated and concentrated to separate out salt is adopted, wherein the concentration of main ions magnesium ions, sodium ions, lithium ions, boron elements and chloride ions contained in the brine is 118g/L, 2.0g/L, 5.0g/L, 3.0g/L and 300g/L respectively, and the specific operation steps are as follows:
and (3) sending the brine into a device filled with an aluminum adsorbent for adsorption, and after the adsorption is finished, sequentially eluting and desorbing, and collecting a lithium-containing desorption solution, wherein the lithium concentration is 1.2g/L.
And (3) sequentially sending the lithium-containing desorption solution into a reverse osmosis membrane and an electrodialysis device for concentration to obtain a lithium-containing concentrated solution, wherein the lithium concentration is 10.3g/L.
And directly sending the lithium-containing desorption solution into a lithium precipitation device, heating to 70 ℃, adding 35wt% of sodium phosphate solution by mass percent, ensuring that the phosphate is excessive by 7wt%, regulating the pH value to 13.0 by using potassium carbonate solution, concentrating by using a 50um ceramic membrane, filtering by using a plate frame, washing by hot water, and drying to obtain white powder, namely the lithium phosphate with the purity of 93.1%.
Wherein, the yield of lithium in the lithium precipitation process is 99.0%.
Example 5
The difference between this example and example 3 is that the brine is sent to a device containing a manganese adsorbent for adsorption, and after the adsorption is completed, the elution and desorption are sequentially performed, and the desorption liquid containing lithium is collected, wherein the lithium concentration is 6.2g/L. Wherein, the yield of lithium in the lithium precipitation process is 98.3 percent.
The other conditions were exactly the same as in example 3.
Example 6
The difference between this example and example 5 is that the desorption solution containing lithium is directly sent into the lithium precipitation device to raise the temperature to 80 ℃, and the mixed solution of dipotassium hydrogen phosphate, potassium dihydrogen phosphate and potassium phosphate with the mass fraction of 30wt% is added to ensure that the phosphate radical is excessive by 8wt%, the pH value is adjusted to 11.0 by ammonia water solution, and the solution is concentrated by a 50um ceramic membrane and then filtered by a plate frame, washed by hot water and dried to obtain white powder, namely the lithium phosphate with the purity of 98.1%. Wherein, the yield of lithium in the lithium precipitation process is 98.0%.
The other conditions were exactly the same as in example 5.
Example 7
The difference between the present example and example 4 is that the concentration of lithium in the brine which is evaporated, concentrated and separated out to form salt is 2.1g/L; directly sending the desorption solution containing lithium into a lithium precipitation device, heating to 80 ℃, adding a mixed solution of diammonium hydrogen phosphate, monoammonium hydrogen phosphate and ammonium phosphate with the mass fraction of 30wt%, ensuring that the phosphate radical is excessive by 6wt%, regulating the pH value to 11.0 by using the mixed solution of ammonium carbonate and ammonium bicarbonate, concentrating by adopting a 50um ceramic membrane, filtering by adopting a plate frame, washing by hot water, and drying to obtain white powder, namely the lithium phosphate with the purity of 93.1%. Wherein, the yield of lithium in the lithium precipitation process is 98.5 percent.
The other conditions were exactly the same as in example 4.
Comparative example 1
This example differs from example 1 in that a sodium carbonate solution having a mass fraction of 25wt% was added to the lithium-containing concentrate to obtain lithium carbonate having a purity of 90.1%, wherein the yield of lithium during precipitation was 35.0%.
Other conditions were exactly the same as in example 1.
Comparative example 2
This example differs from example 2 in that a sodium carbonate solution having a mass fraction of 25wt% was added to the lithium-containing concentrate to obtain lithium carbonate having a purity of 95.6%, wherein the yield of lithium during precipitation was 80.2%.
The other conditions were exactly the same as in example 2.
The main technical indexes in each embodiment of the utility model are shown in table 1.
TABLE 1
Claims (7)
1. A salt lake brine lithium extraction device, characterized by comprising:
an adsorbent tank (1) for adsorbing lithium in brine;
a salt concentration device (3) connected to the adsorbent tank (1) for concentrating the eluent in the adsorbent tank (1);
a reactor (4) connected to the concentration side of the salt concentration device (3) for carrying out lithium precipitation reaction on the concentrated feed liquid;
a phosphate adding tank (5) and an alkali liquor adding tank (6) which are respectively connected with the reactor (4) and are used for adding phosphate and alkali into the reactor (4);
and a solid-liquid separation device (7) connected to the reactor (4) for separating the solid from the liquid of the produced precipitate.
2. The lithium extraction device for salt lake brine according to claim 1, wherein the solid-liquid separation device (7) is one or a combination of a plurality of centrifuges, settling tanks and filters.
3. The lithium extraction device of salt lake brine according to claim 2, wherein the solid-liquid separation device (7) comprises a ceramic membrane (8) and a plate-frame filter (9) which are sequentially connected.
4. The salt lake brine lithium extraction device of claim 1, further comprising: and a dryer (10) connected to the solid-liquid separation device (7) for drying the separated solid.
5. The salt lake brine lithium extraction device of claim 1, further comprising: the eluent is added into the tank (2) and is connected with the adsorbent tank (1) for eluting the adsorbent.
6. The device for extracting lithium from salt lake brine according to claim 1, wherein the salt concentration device (3) is one or a combination of a reverse osmosis membrane, a forward osmosis membrane, electrodialysis and an evaporation device.
7. A salt lake brine lithium extraction device according to claim 3, wherein the ceramic membrane (8) has an average pore size in the range of 20-500nm.
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