CN112142076B - Method for extracting lithium from brine by adsorption method - Google Patents
Method for extracting lithium from brine by adsorption method Download PDFInfo
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- CN112142076B CN112142076B CN202010934840.0A CN202010934840A CN112142076B CN 112142076 B CN112142076 B CN 112142076B CN 202010934840 A CN202010934840 A CN 202010934840A CN 112142076 B CN112142076 B CN 112142076B
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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Abstract
The invention discloses a method for extracting lithium from brine by an adsorption method, which comprises the following steps: adding one or more of fresh water, selected brine and selected compounds into sulfate radical-containing brine to obtain mixed solution; or evaporating and concentrating the sulfate radical-containing brine until the sulfate radical ion content is 8-30 g/L and the sodium ion content is 60-120 g/L, and then freezing to obtain a concentrated solution, so that the sulfate radical ion content in the obtained mixed solution or concentrated solution is reduced to be below 7g/L, and the ratio of the sulfate radical ion content to the total anion content is reduced to be below 4.7 wt%; and adsorbing and desorbing lithium in the mixed solution by adopting an aluminum-based adsorbent, thereby realizing the extraction of the lithium. According to the invention, the efficiency of the aluminum-based adsorbent in the lithium adsorption process is improved by adjusting the content and proportion of sulfate ions in the brine, so that the adsorption and desorption performance of the aluminum-based adsorbent can be improved by about 50-400% in the subsequent lithium extraction adsorption process.
Description
Technical Field
The invention relates to a method for extracting lithium, in particular to a method for adsorbing and extracting lithium from sulfate brine or sulfate-containing brine, belonging to the field of extraction of lithium.
Background
Lithium has become a focus of attention and development as a new strategic energy source. Lithium and its compounds are widely used in many fields such as electronics, metallurgy, chemical industry, medicine, energy and the like due to their excellent properties, have a very important status in national economy and national defense construction, are known as "new energy metal in the 21 st century", and drive the vigorous development of the international lithium market. Currently, the demand for lithium products in the international market is increasing at a rate of 7% to 11% per year and its momentum will continue to remain.
There are two main types of terrestrial lithium resources that have been explored: ore type lithium resources and salt lake lithium resources. Lithium is abundant in salt lake brine, and the cost for extracting lithium from the salt lake is lower than that for extracting lithium from lithium ore, so lithium salt produced by taking salt lake brine as a raw material accounts for more than 70% of lithium products in recent years. The lithium resources proved by China, particularly the lithium resources in salt lakes, are extremely rich, and the prospect reserves are considerable. However, most of the salt lake brine in China has the characteristic of high magnesium/calcium-lithium ratio, and great difficulty is brought to the extraction of lithium. The lithium resources in China are rich and are mainly distributed in Qinghai, Xinjiang, Tibet and the like, but the lithium resources are generally low in grade and relatively high in magnesium and lithium, so that certain challenge is brought to the development of the lithium resources.
The currently reported methods for extracting lithium from salt lake brine mainly include precipitation crystallization, calcination leaching, carbonization, electrochemical method, solvent extraction, adsorption and the like. The adsorption method is one of effective methods for extracting lithium from brine, can avoid series of engineering problems caused by high magnesium/calcium-lithium ratio to a certain extent, and can be carried out under the condition of low lithium ion content. The adsorption method has simple process and high recovery rate, is particularly suitable for separating a system with low target ion concentration and high magnesium/calcium-lithium ratio, and has obvious advantages. At present, the chloride salt lake of Chaolkh realizes the industrialized production. In addition, the aluminum-based adsorbent is stable, is suitable for a high-salinity brine system, has good thermal stability and mechanical stability, adapts to brine temperature difference change and the strength requirement of adsorption operation, and is one of ideal adsorbents. The aluminum-based adsorbent has better economic benefits in treating chloride salt lake brine, but still faces a very big challenge in solving the problem of sulfate salt lake/sulfate-containing brine, especially in treating a sulfate salt lake/sulfate-containing brine system with the sulfate radical content of more than 7g/L, and the main problem is that the adsorption and desorption rates of the adsorbent are low due to the existence of sulfate radicals, so that the industrial production efficiency is low.
Disclosure of Invention
The invention aims to provide a method for extracting lithium from brine by an adsorption method, thereby overcoming the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for extracting lithium from brine by an adsorption method, which comprises the following steps:
adding one or more of fresh water, selected brine and selected compounds into brine containing sulfate radical, so as to reduce the content of sulfate radical ions in the obtained mixed liquor to below 7g/L and reduce the ratio of the content of sulfate radical ions to the total content of anions to below 4.7 wt%;
and adsorbing and desorbing lithium in the mixed solution by adopting an aluminum-based adsorbent to realize the extraction of the lithium.
In some preferred embodiments, the selected brine comprises any one or a combination of two or more of chloride brine, nitrate brine, carbonate brine, and sulfate brine.
In some preferred embodiments, the selected compound comprises any one or a combination of two or more of chloride, nitrate, carbonate, hydroxide.
Further, the pH value of the mixed solution is 3-9.
Further, the content of lithium ions in the mixed solution is less than 1.5 g/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes sulfate type brine or salt lake brine containing sulfate radical as raw material, and takes aluminum-based adsorbent to adsorb and desorb lithium to obtain lithium chloride solution. The method adjusts the content and proportion of sulfate ions in the brine in a mode of adding fresh water, selecting brine or selecting compounds into the brine, or carries out evaporation concentration on the salt lake brine containing sulfate radicals, and then carries out freezing operation, so that the content of the sulfate radicals in the brine is reduced to be below 7g/L, and the ratio of the content of the sulfate radicals to the total content of anions in the solution is lower than 4.7 wt%; moreover, the apparent pH range of the adjusted brine is 3-9, so that the efficiency of the aluminum-based adsorbent in the adsorption process can be improved, the adsorption and desorption performance of the aluminum-based adsorbent can be improved by about 50-400% in the subsequent lithium adsorption and extraction processes, and the problem of low adsorption and desorption efficiency of sulfate brine/sulfate-containing brine in the engineering process is well solved. Compared with untreated brine, the method has the advantage that the adsorption and desorption capacity of the adsorbent can be greatly improved.
Detailed Description
As described above, when a sulfate type salt lake/sulfate-containing brine system having a sulfate group content of 7g/L or more is treated with an aluminum-based adsorbent, there are problems that the adsorption and desorption efficiencies are low. After extensive research, the inventors of the present invention found that the reason why the foregoing problems occur may be that sulfate is present in the adsorbent in the form of lithium sulfate, which has a lower solubility than lithium chloride, resulting in lower adsorption and desorption efficiencies of the adsorbent. Based on the findings, the inventors of the present invention have long studied and practiced a lot of times to provide the technical solutions of the present invention.
In summary, some embodiments of the present invention provide solutions including: the method is characterized in that at least one or more of selected compounds, selected brine and fresh water are added into the sulfate radical-containing brine, or the sulfate radical-containing brine is evaporated, concentrated and frozen to adjust the composition ratio of ions in the sulfate radical-containing brine, particularly the concentration of sulfate radicals and the percentage of sulfate radicals to total anions, so that the efficiency of extracting lithium from the sulfate radical-containing brine by using the aluminum-based adsorbent is improved. The inventors of the present invention have found, quite surprisingly, that when the concentration of sulfate ions in the sulfate-containing brine is reduced to below 7g/L and the percentage of sulfate ions to total anions is reduced to below 4.7wt% by using the embodiments, the adsorption and desorption efficiency of lithium ions in the sulfate-containing brine by the aluminum-based adsorbent is remarkably improved, and the improvement is over 50%. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for extracting lithium from brine by an adsorption method, including:
adding one or more of fresh water, selected brine and selected compounds into sulfate radical-containing brine to obtain mixed solution; or evaporating and concentrating the sulfate radical-containing brine until the sulfate radical ion content is 8-30 g/L and the sodium ion content is 60-120 g/L, and then freezing to obtain a concentrated solution, so that the sulfate radical ion content in the obtained mixed solution or concentrated solution is reduced to be below 7g/L, and the ratio of the sulfate radical ion content to the total anion content is reduced to be below 4.7 wt%;
and (3) adsorbing and desorbing lithium in the mixed solution or the concentrated solution by adopting an aluminum-based adsorbent to realize the extraction of the lithium.
In the foregoing embodiment of the present invention, when the concentration of sulfate ions in the sulfate-containing brine and the proportion of the sulfate ions in the total anions are reduced to 7g/L or less and 4.7wt% or less, respectively, the efficiency of extracting and desorbing lithium from the sulfate-containing brine by the aluminum-based adsorbent can be significantly improved, which may be caused by: when the sulfate radical content in the solution is high, the lithium exists in the adsorbent in the adsorption process in the form of lithium sulfate, the solubility of the lithium sulfate is obviously lower than that of lithium chloride, and the sulfate radical is divalent and has stronger binding capacity in the adsorbent, so the elution process is difficult, and the desorption efficiency is reduced. The content of sulfate radicals is reduced to below 7 g/L; meanwhile, when the content of sulfate radicals accounts for less than 4.7wt% of the total anion content, the influence of the sulfate radicals in the adsorbent is not obvious, so that the adsorption and desorption efficiency is improved.
In some embodiments, the method comprises: diluting the brine in a certain proportion, and then adding a selected compound into the brine or adjusting the content and proportion of sulfate ions in the brine in a selected brine mode; subsequently, an aluminum-based adsorbent is added to the brine to perform adsorption and desorption of lithium in the brine, thereby obtaining a lithium chloride solution.
In some embodiments, the specific steps of the adsorption method for extracting lithium from brine are detailed as follows:
(1) adding fresh water or selected brine or selected compounds or a mixture of the fresh water or the selected brine or the selected compounds into brine containing sulfate radicals, and adjusting the content and the proportion of the sulfate ions in the brine to finally reduce the content of the sulfate ions in the brine to be below 7g/L, wherein the ratio of the sulfate radical content to the total anion concentration content in the solution is lower than 4.7 wt%; moreover, the apparent pH range of the adjusted brine is 3-9, and the influence on the adsorbent when the pH value exceeds the range is avoided;
(2) and adding an aluminum-based adsorbent into the brine to adsorb and desorb lithium in the brine, so as to obtain a lithium chloride solution.
In some preferred embodiments, the brine contains sulfate, and is a sulfate-type brine or a sulfate-containing brine.
In some preferred embodiments, the selected brine added includes, but is not limited to, a mixed brine formed from any one or a combination of two or more of chloride-type brine, nitrate-type brine, carbonate-type brine, sulfate-type brine, and the like.
In some preferred embodiments, the selected compound added includes any one or a combination of two or more of chloride, nitrate, carbonate, hydroxide, and the like, but is not limited thereto.
Further, the chloride includes any one or a combination of two or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride, lead chloride, and the like, but is not limited thereto.
Further, the nitrate salt includes sodium nitrate, potassium nitrate, etc., but is not limited thereto.
Further, the carbonate includes sodium carbonate, calcium carbonate, etc., but is not limited thereto.
Further, the hydroxide includes calcium hydroxide, but is not limited thereto.
In some preferred embodiments, the method comprises: the sulfate ion content in the mixed solution is reduced to 7g/L or less by adding one or a combination of two or more selected from fresh water, a selected brine and a selected compound to the sulfate-containing brine, and the carbonate ion content is preferably controlled to be less than 2g/L because the presence of carbonate forms lithium carbonate to lower the adsorption efficiency. And the ratio of the sulphate content to the total anion content of the solution is less than 4.7 wt%.
Furthermore, the apparent pH value of the mixed solution is in a range of 3-9, preferably 5-7.
Furthermore, the content of lithium ions in the mixed liquid is below 1.5g/L, namely the content of lithium ions in the regulated brine is generally not higher than 1.5g/L, and preferably below 0.5 g/L.
In some embodiments, the present invention provides a method for extracting lithium from brine by an adsorption method, comprising: the brine is concentrated by evaporation, then is simplified by freezing, and then is extracted by using an aluminum-based adsorbent. The method comprises the following specific steps: the method comprises the following steps of evaporating and concentrating brine, then simplifying the brine in a freezing mode, and then extracting lithium in the brine by using an aluminum-based adsorbent: evaporating sulfate type brine/sulfate radical-containing brine, evaporating the sulfate radical ion content of the brine to 8-30 g/L and evaporating the sodium ion content of the brine to 60-120 g/L, freezing the sulfate radical-containing brine, separating out a frozen liquid phase, and adding an aluminum-based adsorbent into the frozen brine to adsorb and desorb lithium ions in the brine to obtain a lithium chloride solution.
In some embodiments, the specific steps of the adsorption process for extracting lithium from brine are detailed as follows:
(1) evaporating and concentrating the sulfate radical-containing brine until the sulfate radical ion content is 8-30 g/L and the sodium ion content is 60-120 g/L;
(2) freezing the system to finish freezing when the sulfate content in the brine system is lower than 7 g/L;
(3) and adding an aluminum-based adsorbent into the frozen brine to adsorb and desorb lithium in the brine, thereby obtaining a lithium chloride solution.
The method takes sulfate type brine/sulfate radical-containing brine as a raw material, carries out brine freezing operation by adjusting the contents of sulfate radicals and sodium ions in the brine, and carries out lithium adsorption and desorption by using an aluminum-based adsorbent to obtain a lithium chloride solution. Compared with untreated brine, the method has the advantage that the adsorption and desorption capacity of the adsorbent can be greatly improved.
In some preferred embodiments, the brine contains sulfate, and is a sulfate-type brine or a sulfate-containing brine.
In some preferred embodiments, in the evaporation concentration stage in step (1), the sulfate ion content is adjusted to 8-30 g/L, and the sodium ion content is adjusted to 60-120 g/L.
In some preferred embodiments, the operation in step (2) is a freezing operation, and the freezing temperature is below-5 ℃, i.e., below-5 ℃.
Further, the sulfate radical content in the frozen brine in the step (2) is lower than 7g/L, the ratio of the sulfate radical content to the total anion content in the solution is lower than 4.7%, and the carbonate radical content in the brine is lower than 2 g/L; moreover, the apparent pH value of the brine is in a range of 3-9, preferably 5-7.
Furthermore, the content of lithium ions in the concentrated solution is below 1.5g/L, namely the content of lithium ions in the adjusted brine is generally not higher than 1.5g/L, and is preferably below 0.5 g/L.
In some preferred embodiments, the adsorbent employed in the present invention is an aluminum-based adsorbent comprising LiCl. mAl (OH)3·nH2O、LiCl·mAl(OH)3·nH2O derivatives or analogs thereof, and the like, but are not limited thereto.
By the preparation process, the invention takes sulfate type brine or salt lake brine containing sulfate as a raw material, and the lithium is absorbed and desorbed by an aluminum-based adsorbent to obtain the lithium chloride solution. The method adjusts the content and proportion of sulfate ions in the brine by adding fresh water, selecting brine or selecting compounds into the brine or by evaporating and concentrating the brine and then freezing the brine, so that the content of sulfate ions in the brine is reduced to be below 7g/L, and the ratio of the sulfate ions to the total anion content in the solution is lower than 4.7 percent; moreover, the apparent pH range of the adjusted brine is 3-9, so that the efficiency of the aluminum-based adsorbent in the adsorption process can be improved, and the adsorption and desorption performance of the aluminum-based adsorbent can be improved by about 50-400% in the subsequent lithium extraction adsorption process. Compared with untreated brine, the method has the advantage that the adsorption and desorption capacity of the adsorbent can be greatly improved.
In conclusion, the invention better solves the problem of low adsorption and desorption efficiency of the sulfate brine/sulfate-containing brine in the engineering process by carrying out pretreatment on the sulfate brine/sulfate-containing brine and then carrying out lithium adsorption and desorption by using the aluminum-based adsorbent.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in further detail below with reference to several preferred embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying the specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The main composition of the raw material sulfate brine used in this example is shown in table 1.
TABLE 1 main composition of sulfate type brine
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 5.99 | 59.31 | 2.06 | 20.66 | 149.75 | 11.74 | 0.95 | 0.23 |
Fresh water is added into the brine system, the sulfate radical content in the brine is adjusted to be lower than 10g/L, and the composition of the diluted sulfate brine is shown in table 2.
TABLE 2 composition of the diluted sulfate brine
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 4.61 | 45.62 | 1.59 | 15.89 | 115.19 | 9.03 | 0.73 | 0.18 |
Subsequently, magnesium chloride hexahydrate solids were added to the brine to yield the brine composition data of table 3.
TABLE 3 brine composition after magnesium chloride addition
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 3.57 | 35.40 | 1.23 | 30.96 | 141.78 | 7.00 | 0.57 | 0.14 |
The concentration ratio of sulfate radical in the magnesium chloride-added solution was 4.7%, and at this time, the pH of the solution was about 6.5, and LiCl.2Al (OH) was added to the magnesium chloride-added brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 4.5mg/g, and the adsorption and desorption efficiency is improved by about 50% compared with untreated brine.
If a sodium nitrate solution is added to the solution, brine composition data of Table 4 is obtained.
TABLE 4 brine composition after sodium nitrate addition
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | Li+ | NO3 - |
| Content (g/L) | 3.54 | 97.40 | 1.22 | 12.23 | 88.61 | 6.95 | 0.14 | 168.46 |
The ratio of sulfate concentration in the brine after the addition of sodium nitrate was 2.6%, at which point the solution had a pH of about 6.5. Adding LiCl 2Al (OH) into brine after adding sodium nitrate3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 5mg/g, and the adsorption and desorption efficiency is improved by about 67% compared with that of untreated brine.
If potassium nitrate is added to the brine, the adsorption and desorption effects are substantially the same as those of the sodium nitrate.
Example 2
The main composition data of the raw material sulfate brine adopted in the present example are shown in table 5.
TABLE 5 data on the main composition of the sulphate brine
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 9.93 | 90.96 | 1.425 | 33.51 | 242.19 | 12.06 | 1.77 | 0.36 |
Brine with the composition shown in table 6 was added to the brine system and mixed to obtain mixed brine with the composition shown in table 7.
TABLE 6 composition of brine to be added
| Components | K+ | Na+ | CO3 2- | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 6.28 | 86.64 | 6.24 | 0.28 | 130.62 | 4.90 | 1.85 | 0.47 |
TABLE 7 Mixed brine composition
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 8.11 | 88.80 | 0.20 | 15.6 | 186.41 | 7.00 | 1.81 | 0.41 |
The pH of the mixed brine after the carbonate brine is added is about 7.2, and the concentration ratio of sulfate radicals in the solution is 3.6%. Adding LiCl 2Al (OH) into brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 7mg/g, and the adsorption and desorption efficiency is improved by about 75% compared with that of untreated brine.
Then, a small amount of water and sodium chloride are added into the brine, the content and proportion of sulfate radicals in the brine are continuously adjusted, the composition of the brine after adjustment is shown in table 8, the pH of the brine is 6.8, and the concentration proportion of the sulfate radicals in the solution is 3.2%.
TABLE 8 brine adjusted composition
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 6.37 | 106.89 | 0.16 | 12.26 | 203.81 | 6.67 | 1.42 | 0.33 |
Adding LiCl 2Al (OH) into the brine after adding sodium chloride3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 9mg/g, and the adsorption and desorption efficiency is improved by about 125% compared with that of untreated brine.
If potassium chloride is added to the system, the adsorption and desorption effects are substantially the same as with the addition of sodium chloride.
Example 3
The data for the main composition of the raw sulfate-containing brine used in this example are shown in table 9.
TABLE 9 data on the main composition of bittern containing sulfate
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 0.76 |
The composition of another sulfate-containing brine is shown in table 10.
TABLE 10 other main composition data of sulfate-containing brine
Two sulfate-containing brines were mixed in a ratio of 1: 1.5, the brine composition after mixing is shown in table 11. At this point, the brine had a pH of about 6.4 and the sulfate concentration in the solution was 3.2%.
TABLE 11 Mixed brine composition
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 6.16 | 63.08 | 8.46 | 203.76 | 6.74 | 0.484 |
Adding LiCl 2Al (OH) into the mixed brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 10mg/g, and the adsorption and desorption efficiency is improved by about 67% compared with untreated brine.
Example 4
The data for the main composition of the raw sulfate-containing brine used in this example are shown in table 12.
TABLE 12 data on the main composition of bittern containing sulfate
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 1.50 |
Brine having the composition of table 13 was added to the brine.
TABLE 13 composition of brine to be added
| Components | Na+ | Mg2+ | K+ | Cl- | Ca2+ | Li+ |
| Content (g/L) | 3.43 | 3.13 | 13.17 | 326.56 | 169.40 | 1.42 |
The brine composition data after mixing is shown in table 14.
TABLE 14 Mixed brine composition
| Components | Na+ | Mg2+ | K+ | Cl- | Ca2+ | Li+ |
| Content (g/L) | 0.50 | 66.94 | 0.74 | 213.12 | 0.20 | 1.50 |
The apparent pH value of the mixed brine is about 3, and the concentration ratio of sulfate radicals in the solution is 0%. Adding LiCl 2Al (OH) into the mixed brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 11mg/g, and the adsorption and desorption efficiency is improved by about 57% compared with that of untreated brine.
Example 5
The data for the main composition of the raw sulfate-containing brine used in this example are shown in table 15.
TABLE 15 data on the main composition of bittern containing sulfate
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 0.76 |
The slaked lime water solution was added to the brine to adjust the solution composition, and the data of the mixed brine composition are shown in table 16.
Table 16 brine blend composition data
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.36 | 60.10 | 0.27 | 190.09 | 4.80 | 0.69 |
The apparent pH of the mixed brine is about 9, and the concentration ratio of sulfate radical in the solution is 2.5%. Adding LiCl 2Al (OH) into the mixed brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 8mg/g, and the adsorption and desorption efficiency is improved by about 78% compared with untreated brine.
Example 6
The data for the main composition of the raw sulfate-containing brine used in this example are shown in Table 17.
TABLE 17 data on the main composition of bittern containing sulfate
| Components | K+ | Mg2+ | Cl- | CO3 2- | SO4 2- | B2O3 | Li+ | Na+ |
| Content (g/L) | 10.26 | 0.1 | 179.1 | 8.61 | 7.47 | 3.4 | 0.77 | 116.9 |
The main composition of the brine to be added is shown in Table 18.
TABLE 18 composition of brine to be added
| Components | K+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ | Na+ |
| Content (g/L) | 3.46 | 11.17 | 82.35 | 4.9 | 0.62 | 0.118 | 31.96 |
The composition of the brine after mixing in a ratio of 4:1 is shown in table 19.
TABLE 19 Mixed brine composition
| Components | K+ | Mg2+ | Cl- | CO3 2- | SO4 2- | B2O3 | Li+ | Na+ |
| Content (g/L) | 7.12 | 0.67 | 136.80 | 2.00 | 6.96 | 2.84 | 0.64 | 79.93 |
The pH of the mixed brine is about 7.8, and the concentration ratio of sulfate radical in the solution is 4.5%. Adding LiCl 2Al (OH) into the mixed brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 6mg/g, and the adsorption and desorption efficiency is improved by about 400% compared with that of untreated brine.
From the above examples 1 to 6, it can be seen that the present invention can better improve the adsorption and desorption efficiency of the sulfate brine/sulfate-containing brine by adjusting the parameters such as sulfate radical concentration and the like and using the aluminum-based adsorbent.
Example 7
The main composition of the raw material sulfate brine used in this example is shown in table 1.
The composition of the adjusted brine obtained by adding calcium chloride to the brine is shown in table 20.
TABLE 20 adjusted brine Main composition
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 5.91 | 58.55 | 0.84 | 20.39 | 156.40 | 0.20 | 0.94 | 0.22 |
The proportion of sulfate concentration in the solution after the addition of calcium chloride was 0.13%, at which time the solution had a pH of about 7.2. Adding LiCl 2Al (OH) into the mixed brine3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 7mg/g, and the adsorption and desorption efficiency is improved by about 133% compared with untreated brine.
If barium chloride is added to the solution, the effect is substantially the same as with the addition of calcium chloride.
Example 8
The raw brine is shown in table 1, and sodium carbonate is added to the brine to obtain the adjusted brine shown in table 21.
TABLE 21 adjusted brine Main composition
| Components | K+ | Na+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 5.46 | 101.28 | 136.51 | 10.70 | 0.87 | 0.21 |
Lead chloride was then added to the brine to give the brine composition shown in table 22.
TABLE 22 adjusted brine Main composition
| Components | K+ | Na+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 5.38 | 99.78 | 149.49 | 5.35 | 0.85 | 0.20 |
The ratio of sulfate concentration in the solution after the addition of lead chloride was 3.7%, at which time the solution had a pH of about 7.1. Adding LiCl 2Al (OH) into the mixed brine3·nH2And adsorbing and desorbing the brine by using the O adsorbent to obtain a lithium chloride solution, wherein the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 8.5mg/g, and the adsorption and desorption efficiency is improved by about 183% compared with that of untreated brine.
Comparative example 1
TABLE 1 main composition of sulfate type brine
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 5.99 | 59.31 | 2.06 | 20.66 | 149.75 | 11.74 | 0.95 | 0.23 |
According to the brine composition data in Table 1, LiCl.2Al (OH) was added to untreated brine without the addition of fresh water, magnesium chloride or sodium nitrate3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, and the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 3mg/g and is far lower than that of the treated brine.
Comparative example 2
TABLE 5 data on the main composition of the sulphate brine
| Components | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | B2O3 | Li+ |
| Content (g/L) | 9.93 | 90.96 | 1.425 | 33.51 | 242.19 | 12.06 | 1.77 | 0.36 |
According to the brine composition data of Table 5, LiCl2 Al (O) was added directly to the brineH)3·nH2Adsorbing and desorbing brine by using an O adsorbent to obtain a lithium chloride solution, wherein the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 4 mg/g; and the adsorption and desorption capacities of the adsorbent of the brine added with carbonate or sodium chloride are respectively improved by 75 percent and 125 percent. Therefore, the adsorption and desorption efficiency can be obviously improved by adjusting the sulfate radical content and the proportion of the brine.
Comparative example 3
TABLE 9 data on the main composition of bittern containing sulfate
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 0.76 |
LiCl 2Al (OH) was added directly to the brine according to the brine composition of Table 93·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the balanced adsorption and desorption capacity of the lithium chloride solution is about 6mg/g, and the adsorption and desorption capacity of the adjusted brine is 10mg/g, which is improved by 67%.
Comparative example 4
TABLE 12 data on the main composition of the sulfate-containing brines
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 1.50 |
Brine composition according to table 12, directly to brineAdding LiCl 2Al (OH)3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 7mg/g, and the adsorption and desorption capacity of the adjusted brine is 11mg/g, which is improved by 57%.
Comparative example 5
TABLE 15 data on the main composition of bittern containing sulfate
| Components | Na+ | Mg2+ | K+ | Cl- | SO4 2- | Li+ |
| Content (g/L) | 0.40 | 69.20 | 0.30 | 209.10 | 14.30 | 0.76 |
LiCl 2Al (OH) was added directly to the brine according to the brine composition of Table 153·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 4.5mg/g, and the adsorption and desorption capacity of the adjusted brine is 8mg/g, which is improved by 77%.
Comparative example 6
TABLE 17 data on the main composition of bittern containing sulfate
| Components | K+ | Mg2+ | Cl- | CO3 2- | SO4 2- | B2O3 | Li+ | Na+ |
| Content (g/L) | 10.26 | 0.1 | 179.1 | 8.61 | 7.47 | 3.4 | 0.77 | 116.9 |
LiCl 2Al (OH) was added directly to the brine according to the brine composition of Table 173·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, the balanced adsorption and desorption capacity of the lithium chloride solution is about 1.2mg/g, and the adsorption and desorption capacity of the adjusted brine is 6mg/g and is improved by 400%.
Example 9
The data for the main composition of the raw sulfate-containing brine used in this example are shown in table 23.
TABLE 23 data on the main composition of the bittern containing sulfate
(1) Evaporating and concentrating the sulfate-containing brine to adjust the sulfate ion content of the brine to be about 10g/L and the sodium ion content to be about 60 g/L.
(2) And (3) freezing the brine system at the temperature of-25 ℃, and finishing freezing when the content of sulfate ions in the brine is 4g/L and the concentration ratio of sulfate ions is 3.96%, wherein the apparent pH value of the brine is about 6.7, and the content of lithium ions in the solution is 0.28 g/L.
(3) Adding LiCl 2Al (OH) into the frozen brine3·nH2The O adsorbent is used for absorbing and desorbing lithium to obtain a lithium chloride solution, and compared with untreated brine, the absorption and desorption capacity is improved by about 67 percent and reaches 5 mg/g.
Example 10
The principal composition of the feed sulfate-containing brine used in this example is shown in the brine data in example table 23.
(1) Evaporating and concentrating the sulfate-containing brine to adjust the sulfate ion content of the brine to be about 15g/L and the sodium ion content to be about 100 g/L.
(2) And (3) freezing the brine system at the temperature of-5 ℃, and finishing freezing when the content of sulfate ions in the brine is 7g/L and the concentration ratio of sulfate ions is 4.63%, wherein the apparent pH value of the brine is about 6.9, and the content of lithium ions in the solution is 0.28 g/L.
(3) Adding LiCl 2Al (OH) into the frozen brine3·nH2The O adsorbent is used for absorbing and desorbing lithium to obtain a lithium chloride solution, and compared with untreated brine, the absorption and desorption capacity can be improved by about 100 percent to 6 mg/g.
Example 11
The main composition of the raw sulfate containing brine used in this example is shown in example table 23.
(1) Evaporating and concentrating the sulfate-containing brine at high temperature, and adjusting the sulfate ion content of the brine to be about 30g/L and the sodium ion content to be about 120 g/L.
(2) And (3) freezing the brine system at the temperature of-15 ℃, and finishing freezing when the content of sulfate ions in the brine is 4g/L and the concentration ratio of sulfate ions is 1.73%, wherein the apparent pH value of the brine is about 6.7 and the content of lithium ions in the solution is 1.0 g/L.
(3) Adding LiCl 2Al (OH) into the frozen brine3·nH2The O adsorbent is used for adsorbing and desorbing lithium to obtain a lithium chloride solution, and compared with untreated brine, the adsorption and desorption capacity can be improved by about 153% to 7.6 mg/g.
Example 12
The data for the main composition of the raw sulfate-containing brine used in this example are shown in Table 24.
TABLE 24 data on the main composition of bittern containing sulfate
(1) Evaporating and concentrating the sulfate-containing brine to adjust the sulfate ion content of the brine to be about 8g/L and the sodium ion content to be about 110 g/L.
(2) Freezing the brine system at the temperature of minus 20 ℃, and finishing freezing when the content of sulfate ions in the brine is lower than 2g/L and the content of carbonate ions is about 2 g/L; in this case, the concentration ratio of sulfate was 1.52%, the apparent pH of the brine was about 9, and the content of lithium ions in the solution was 0.87 g/L.
(3) Adding LiCl 2Al (OH) into the frozen brine3·nH2The O adsorbent is used for absorbing and desorbing lithium to obtain a lithium chloride solution, and compared with untreated brine, the absorption and desorption capacity is improved by about 167% and reaches 8 mg/g.
Example 13
The data for the main composition of the raw sulfate-containing brine used in this example are shown in table 25.
TABLE 25 data on the main composition of bittern containing sulfate
(1) Evaporating and concentrating the sulfate-containing brine to adjust the sulfate ion content of the brine to be about 25g/L and the sodium ion content to be about 80 g/L.
(2) And (3) freezing the brine system at the temperature of-10 ℃, and finishing freezing when the sulfate ion content in the brine is 7g/L, wherein the apparent pH value of the brine is about 3, the ratio of the sulfate ion content to the total anion content in the solution is about 4.7%, and the lithium ion concentration in the brine is about 1.5 g/L.
(3) Adding LiCl 2Al (OH) into the frozen brine3·nH2The O adsorbent is used for adsorbing and desorbing lithium to obtain a lithium chloride solution, and compared with untreated brine, the adsorption and desorption capacity is improved by about 200% to 9 mg/g.
From the above examples 9 to 13, it is understood that the adsorption and desorption efficiency of the sulfate brine/sulfate-containing brine can be improved by adjusting the parameters such as the component concentration and the freezing temperature using the aluminum-based adsorbent.
Comparative example 7
As is clear from the brine composition shown in Table 23, LiCl 2Al (OH) was added to the untreated brine without concentration by evaporation3·nH2Adsorbing and desorbing brine by using O adsorbent to obtain lithium chloride solutionThe equilibrium adsorption and desorption capacity is about 3mg/g, which is much lower than that of the treated brine. For another example, if the brine shown in Table 23 is concentrated by evaporation, LiCl 2Al (OH) is added to the solution3·nH2The O adsorbent is used for adsorbing and desorbing the brine to obtain a lithium chloride solution, and the equilibrium adsorption and desorption capacity of the lithium chloride solution is about 4mg/g and is far lower than that of the treated brine.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where compositions are described as having, containing, or comprising specific components, or where processes are described as having, containing, or comprising specific process steps, it is contemplated that compositions taught by the present invention also consist essentially of, or consist of, the recited components, and that processes taught by the present invention also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventor also carries out corresponding tests by using other process conditions and the like listed in the foregoing to replace the corresponding process conditions in the examples 1 to 13, and the contents to be verified are similar to the products of the examples 1 to 13. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 13 are used as representatives to describe the excellent points of the present invention.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (7)
1. A method for extracting lithium from brine by an adsorption method is characterized by comprising the following steps:
adding one or more of fresh water, selected brine and selected compounds into sulfate radical-containing brine to obtain mixed solution; or evaporating and concentrating the brine containing sulfate radicals until the content of sulfate radical ions is 8-30 g/L and the content of sodium ions is 60-120 g/L, and then freezing to obtain a concentrated solution; thereby reducing the content of sulfate ions in the obtained mixed solution or concentrated solution to below 7g/L and reducing the ratio of the content of the sulfate ions to the total content of anions to below 4.7 wt%; wherein the selected brine comprises one or more of chloride brine, nitrate brine, carbonate brine and sulfate brine; the selected compound comprises any one or a combination of two or more of chloride, nitrate, carbonate and hydroxide, the chloride comprises any one or a combination of two or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride and lead chloride, the nitrate comprises sodium nitrate and/or potassium nitrate, the carbonate comprises sodium carbonate and/or calcium carbonate, and the hydroxide comprises calcium hydroxide; the pH value of the mixed solution or the concentrated solution is 3-9; the content of lithium ions in the mixed solution or the concentrated solution is below 1.5 g/L;
and (3) adsorbing and desorbing lithium in the mixed solution or the concentrated solution by adopting an aluminum-based adsorbent to realize the extraction of the lithium.
2. The method of claim 1, wherein: the temperature adopted by the freezing treatment is below-5 ℃.
3. The method of claim 1, comprising: adding one or more of fresh water, selected brine and selected compounds into sulfate radical-containing brine; or evaporating and concentrating the sulfate radical-containing brine until the sulfate radical ion content is 8-30 g/L and the sodium ion content is 60-120 g/L, and then freezing; thereby reducing the content of carbonate ions in the obtained mixed solution or concentrated solution to below 2 g/L.
4. The method of claim 1, wherein: the pH value of the mixed solution or the concentrated solution is 5-7.
5. The method of claim 1, wherein: the content of lithium ions in the mixed solution or the concentrated solution is below 0.5 g/L.
6. The method of claim 1, further comprising: after the freezing treatment is finished, separating out a freezing liquid phase to obtain the concentrated solution, and adding an aluminum-based adsorbent into the concentrated solution.
7. The method of claim 1, wherein: the aluminum-based adsorbent comprises LiCl mAl (OH)3·nH2O and/or LiCl mAl (OH)3·nH2And (3) an O derivative.
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