CN115124054A - Method for separating and extracting rubidium and cesium salt from lepidolite lithium precipitation mother liquor - Google Patents
Method for separating and extracting rubidium and cesium salt from lepidolite lithium precipitation mother liquor Download PDFInfo
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Abstract
The invention provides a method for separating and extracting rubidium and cesium salt from lepidolite lithium precipitation mother liquor, which comprises the following steps: firstly, acidifying precipitated lithium mother liquor to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH value meets the requirement, and enriching rubidium and cesium in the precipitated lithium mother liquor to obtain a rubidium and cesium salt solution; secondly, alkalizing a rubidium-cesium salt solution and carrying out primary extraction and separation to obtain a cesium-loaded organic phase and a rubidium salt solution of primary extraction residual liquid; and thirdly, carrying out first back extraction crystallization separation on the cesium-loaded organic phase to obtain cesium salt, alkalizing the rubidium salt solution, carrying out second extraction separation to obtain a rubidium-loaded organic phase and a second extraction residual liquid, returning the second extraction residual liquid for use, and carrying out second back extraction crystallization separation on the rubidium-loaded organic phase to obtain rubidium salt. The method simplifies the process flow, meets the environmental protection requirement of zero discharge of wastewater, and remarkably improves the recovery rate of rubidium and cesium salt, so that the recovery rate of rubidium and cesium salt exceeds 99 percent.
Description
Technical Field
The invention belongs to the technical field of extracting rubidium and cesium salts from lepidolite, and particularly relates to a method for separating and extracting rubidium and cesium salts from a lepidolite lithium precipitation mother solution.
Background
The rubidium and cesium resources in China are rich, and the rubidium and cesium resources in a solid form are mainly distributed in lepidolite, pollucite and cesium silicon; rubidium and cesium resources existing in liquid form are mainly distributed in salt lakes and geothermal water of the Qinghai, Tibet and the like. Separation of rubidium and cesium is achieved in aqueous solution regardless of whether the initial output form is solid ore or liquid ore. Rubidium and cesium have unique properties, so that rubidium and cesium have important applications in many fields, not only many traditional application fields, but also new application fields, particularly high-tech fields, and the rubidium and cesium show more and more important functions. The comprehensive utilization of rubidium and cesium valuable metals can generate considerable economic benefits.
Rubidium and cesium are used as rare nonferrous metals, and both metal elements are typical dispersed elements and rarely form separate minerals. At present, methods for separating and extracting rubidium and cesium from lepidolite lithium precipitation mother liquor mainly comprise a precipitation method, an ion exchange method, a solvent extraction method and the like; wherein, the precipitation method has long flow, low recovery rate and low product purity, and is mainly used for analysis test or crude product purification; the ion exchange method has the advantages of simple process, good selectivity and high recovery rate, but the exchange capacity of the ion exchanger is relatively small, so that the method is suitable for separating and extracting low-concentration rubidium and cesium; the solvent extraction method has large processing capacity and good production continuity, and is a separation and extraction technology which is researched more and developed more quickly. However, the solvent extraction method in the prior art has complex extraction process and low recovery rate of rubidium and cesium salts in the extracted solid phase, which results in high production cost and large discharge amount of three wastes in environmental protection.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for separating and extracting rubidium and cesium salt from lepidolite lithium deposition mother liquor, which not only simplifies the process flow, realizes the zero discharge and environmental protection requirements of wastewater, but also obviously improves the recovery rate of the rubidium and cesium salt, so that the recovery rate of the rubidium and cesium salt in an extraction solid phase exceeds 99 percent.
The invention provides a method for separating and extracting rubidium and cesium salt from lepidolite lithium precipitation mother liquor, which comprises the following steps:
1) acidifying lepidolite lithium precipitation mother liquor to obtain an acidified solution, adding alkali into the acidified solution to adjust the acidified solution to obtain an alkalized solution with the pH value of 8-10, concentrating the alkalized solution, performing solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, cooling the concentrated solution, and performing solid-liquid separation to obtain a rubidium-cesium salt solution and a second potassium sodium salt; wherein, the first potassium sodium salt and the second potassium sodium salt can be used for lepidolite roasting ingredients;
2) adding alkali into a rubidium-cesium salt solution to adjust the pH value to 10-12, and performing primary extraction and separation to obtain a rubidium salt solution loaded with a cesium organic phase and a primary extraction residual liquid;
3) carrying out first washing, back extraction and crystallization separation treatment on the cesium-loaded organic phase to obtain cesium salt;
4) adding alkali into the rubidium salt solution to adjust the pH value to 12-14, and performing second extraction and separation to obtain a rubidium-loaded organic phase and a second extraction residual liquid, wherein the second extraction residual liquid returns to a lithium precipitation workshop;
5) and carrying out secondary washing, back extraction and crystallization separation treatment on the rubidium-loaded organic phase to obtain a rubidium salt.
Compared with the prior art, the invention has the beneficial effects that: firstly, acidifying precipitated lithium mother liquor to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH meets the requirement, and enriching rubidium and cesium in the precipitated lithium mother liquor to obtain a rubidium and cesium salt solution; secondly, basifying a rubidium-cesium salt solution and carrying out primary extraction separation to obtain a rubidium salt solution loaded with a cesium organic phase and a primary extraction residual liquid; and thirdly, carrying out primary washing, back extraction and crystallization separation on the cesium-loaded organic phase to obtain cesium salt, alkalizing the rubidium salt solution, carrying out secondary extraction separation to obtain a rubidium-loaded organic phase and a secondary extraction raffinate, returning the secondary extraction raffinate to use, and carrying out secondary washing, back extraction and crystallization separation on the rubidium-loaded organic phase to obtain rubidium salt. The process method simplifies the process flow, meets the environmental protection requirement of zero discharge of wastewater, and obviously improves the recovery rate of rubidium and cesium salt, so that the recovery rate of rubidium and cesium salt in the extraction solid phase exceeds 99 percent.
Preferably, the acidizing fluid in the step 1) is obtained by adding sulfuric acid with a preset concentration into the lepidolite lithium precipitation mother liquor, and the pH value is 1-4.
Preferably, the first extraction is carried out by adopting a first organic solvent for extraction treatment, the extraction time is 3-5 min, and the ratio of an extraction organic phase to water is (1-2): 1; the first organic solvent consists of an extracting agent and a diluent, and the volume ratio of the extracting agent to the diluent is 2: 1.
Preferably, the specific steps of the first washing, back extraction and crystallization separation treatment all comprise:
washing treatment: washing the cesium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
back extraction treatment: carrying out back extraction on the washed cesium-loaded organic phase by using sulfuric acid or nitric acid as back extraction acid, wherein the back extraction time is 3-5 min, and the ratio of the back extraction organic phase to water is 15: 1; obtaining a cesium salt stripping solution and a first blank organic phase, wherein the first blank organic phase is recycled;
and (3) crystallization separation: and concentrating the cesium salt back extraction solution until crystals are separated out, cooling to 25-35 ℃, performing solid-liquid separation to obtain cesium salt and a first filtrate, and drying the cesium salt to obtain a cesium sulfate product or a cesium nitrate product.
Preferably, the second extraction is carried out by adopting a second organic solvent for extraction treatment, the extraction time is 3-5 min, and the ratio of the extraction organic phase to water is (1-5): 1; the first organic solvent consists of an extracting agent and a diluent, and the volume ratio of the extracting agent to the diluent is 3: 2.
Preferably, the extractant consists of t-BAMBP and sulfonated kerosene.
Preferably, the volume ratio of the t-BAMBP to the sulfonated kerosene is 2: 1.
Preferably, the specific steps of the second washing, back extraction and crystallization separation treatment all comprise:
washing treatment: washing the rubidium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing liquid, and returning the second washing liquid to a lithium precipitation workshop;
back extraction treatment: carrying out back extraction on the washed rubidium-loaded organic phase by using sulfuric acid or nitric acid as back extraction acid, wherein the back extraction time is 3-5 min, and the ratio of the back extraction organic phase to water is 15: 1; obtaining a rubidium salt stripping solution and a second blank organic phase, wherein the second blank organic phase is recycled;
and (3) crystallization separation: and concentrating the rubidium salt stripping solution until crystals are precipitated, cooling to 25-35 ℃, performing solid-liquid separation to obtain a rubidium salt and a second filtrate, drying the rubidium salt to obtain a rubidium sulfate product or a rubidium nitrate product, and returning the second filtrate to a lithium precipitation workshop.
Preferably, the alkali-adding adjustment treatment in the step 2) and the step 7) is performed by adding flake sodium hydroxide for alkalization.
Preferably, the alkalization solution is obtained by adding flake sodium hydroxide or liquid sodium hydroxide into the acidified lepidolite lithium precipitation mother liquor.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the embodiments or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings may be obtained according to these drawings without inventive labor.
Fig. 1 is a flow chart of a method for separating and extracting rubidium and cesium salts from a lepidolite lithium precipitation mother liquor according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the embodiments of the present invention and should not be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of the present invention, "a plurality" means two or more unless specifically limited otherwise.
As shown in fig. 1, a method for separating and extracting rubidium and cesium salts from a lepidolite lithium precipitation mother liquor is provided in the embodiments of the present application, and includes the following steps:
s01, acidifying the lepidolite lithium precipitation mother liquor to obtain an acidified solution, adding alkali into the acidified solution to adjust the acidified solution to obtain an alkalified solution with the pH value of 8-10, concentrating the alkalified solution, performing solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, cooling the concentrated solution, and performing solid-liquid separation to obtain a rubidium-cesium salt solution and a second potassium sodium salt; wherein, the first potassium sodium salt and the second potassium sodium salt can be used for the lepidolite roasting ingredient.
The acidizing solution is obtained by adding sulfuric acid with a preset concentration into the lithium precipitation mother solution of the lepidolite, and the pH value is 1-4. The alkalization liquid is obtained by adding flaky sodium hydroxide or liquid sodium hydroxide into the acidified lepidolite lithium precipitation mother liquor.
Specifically, the lithium precipitation mother liquor acidification treatment of the lepidolite is to remove carbonate in the lithium precipitation mother liquor of the lepidolite. And after concentration, solid-liquid separation is to remove most of potassium and sodium salts in the lithium precipitation mother liquor of lepidolite, and after cooling, solid-liquid separation is to enrich rubidium and cesium in the lithium precipitation mother liquor.
S02, adding alkali into the rubidium-cesium salt solution to adjust the pH value to 10-12, and performing primary extraction and separation to obtain a rubidium salt solution loaded with a cesium organic phase and a primary extraction residual liquid.
Wherein the first extraction is to adopt a first organic solvent for extraction treatment, the extraction time is 3-5 min, and the ratio of an extraction organic phase to water is (1-2): 1; the first organic solvent consists of an extracting agent and a diluent, and the volume ratio of the extracting agent to the diluent is 2: 1.
Specifically, the treatment of alkalifying the rubidium-cesium salt solution is performed by adding flaky sodium hydroxide to perform alkalization. The extractant consists of t-BAMBP and sulfonated kerosene, and the volume ratio of the t-BAMBP to the sulfonated kerosene is 2: 1.
And S03, carrying out first washing, back extraction and crystallization separation treatment on the cesium-loaded organic phase to obtain the cesium salt.
Wherein, the specific steps of the first washing, the back extraction and the crystallization separation treatment all comprise:
washing treatment: washing the cesium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
back extraction treatment: carrying out back extraction on the washed cesium-loaded organic phase by using sulfuric acid or nitric acid as back extraction acid, wherein the back extraction time is 3-5 min, and the phase ratio of the back extraction organic phase to water is 15: 1; obtaining cesium salt stripping solution and a first blank organic phase, wherein the first blank organic phase is recycled;
and (3) crystallization separation: and concentrating the cesium salt back extraction solution until crystals are separated out, cooling to 25-35 ℃, performing solid-liquid separation to obtain cesium salt and a first filtrate, and drying the cesium salt to obtain a cesium sulfate product or a cesium nitrate product.
And S04, adding alkali into the rubidium salt solution to adjust the pH value to 12-14, performing second extraction and separation to obtain a rubidium-loaded organic phase and a second extraction residual liquid, and returning the second extraction residual liquid to a lithium precipitation workshop.
Wherein the second extraction is to adopt a second organic solvent for extraction treatment, the extraction time is 3-5 min, and the ratio of the extraction organic phase to water is (1-5): 1; the first organic solvent consists of an extracting agent and a diluting agent, and the volume ratio of the extracting agent to the diluting agent is 3: 2.
Specifically, the rubidium salt solution is subjected to an alkalization treatment by adding flake sodium hydroxide. The extractant consists of t-BAMBP and sulfonated kerosene, and the volume ratio of the t-BAMBP to the sulfonated kerosene is 2: 1.
And S05, carrying out secondary washing, back extraction and crystallization separation treatment on the rubidium-loaded organic phase to obtain a rubidium salt.
Wherein, the specific steps of the second washing, the back extraction and the crystallization separation treatment all comprise:
washing treatment: washing the rubidium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing liquid, and returning the second washing liquid to a lithium precipitation workshop;
back extraction treatment: sulfuric acid or nitric acid is used as back extraction acid to carry out back extraction on the washed rubidium-loaded organic phase, the back extraction time is 3 min-5 min, and the ratio of the back extraction organic phase to water is 15: 1; obtaining a rubidium salt stripping solution and a second blank organic phase, wherein the second blank organic phase is recycled;
and (3) crystallization separation: and concentrating the rubidium salt stripping solution until crystals are precipitated, cooling to 25-35 ℃, performing solid-liquid separation to obtain a rubidium salt and a second filtrate, drying the rubidium salt to obtain a rubidium sulfate product or a rubidium nitrate product, and returning the second filtrate to a lithium precipitation workshop.
It should be noted that the components of the lithium precipitating mother liquor of lepidolite used in the following examples are shown in table 1.
TABLE 1
| Composition (A) | Li | Na | K | Rb | Cs | SO 4 2- | C0 3 2- |
| Content (g/L) | 2.56 | 32.98 | 5.03 | 2.51 | 0.54 | 180.21 | 3.45 |
Example 1
The method comprises the following steps: weighing 1.0L of lepidolite lithium precipitation mother liquor reaction kettle, adding sulfuric acid with the concentration of 98% into the reaction kettle, and preferably measuring the pH value of the lithium precipitation mother liquor in the reaction kettle to be 1-4 to obtain an acidizing fluid;
adding flaky sodium hydroxide into the acidizing fluid in the reaction kettle, wherein the addition amount is preferably measured to obtain that the pH value of the lithium precipitation mother liquor in the reaction kettle is 8-10, so as to obtain alkalizing fluid;
concentrating the alkalized solution by adopting a concentration separation technology, carrying out solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, and recycling the first potassium sodium salt for use in lepidolite roasting ingredients;
after the concentrated solution is subjected to cooling treatment, solid-liquid separation is performed to obtain a rubidium-cesium salt solution and a second potassium sodium salt, the components of the rubidium-cesium salt solution are measured, the measurement results are shown in table 2, and the second potassium sodium salt is recycled and used for lepidolite roasting ingredients.
Step two: placing the separated rubidium-cesium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of lithium precipitation mother liquor in a reaction kettle to be 10-12, adding a first organic solvent with the volume ratio of an extracting agent to a diluting agent being 2:1 into the extraction tank to perform countercurrent extraction treatment on the rubidium-cesium salt solution, extracting for 5min, and measuring the components of the rubidium salt solution, wherein the ratio of an extraction organic phase to a water phase is 2:1, so that a rubidium salt solution loaded with a cesium organic phase and a first extraction residual liquid is obtained, and the measurement results are shown in table 2. Wherein the extractant consists of t-BAMBP and sulfonated kerosene with the volume ratio of 2: 1.
Step three: carrying out countercurrent washing on the cesium-loaded organic phase by using distilled water for 5min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
back-extracting the washed cesium-loaded organic phase by using sulfuric acid with the concentration of 98% as back-extraction acid for 5min, wherein the ratio of the back-extraction organic phase to water is 15:1, obtaining a cesium salt back-extraction solution and a first blank organic phase, measuring the components of the cesium salt back-extraction solution, and recycling the first blank organic phase, wherein the measurement results are shown in table 2;
the cesium salt stripping solution is concentrated until crystals are separated out, solid-liquid separation is carried out after the crystals are cooled to 25 ℃, cesium salt and first filtrate are obtained, cesium salt is dried to obtain cesium sulfate products, components of the dried cesium salt are measured, and the measurement results are shown in table 3, and it can be known from table 3 that the content of cesium sulfate-containing products in the obtained cesium salt is more than 99% by the method.
Step four: placing the separated rubidium salt solution into an extraction tank, adding sheet sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of a lithium precipitation mother solution in a reaction kettle to be 12-14, adding a second organic solvent with the volume ratio of an extracting agent to a diluting agent being 3:2 into the extraction tank to perform extraction treatment on the rubidium-cesium salt solution, extracting for 5min, wherein the ratio of an extraction organic phase to a water phase is 5:1, obtaining a rubidium-loaded organic phase and a second extraction residual liquid, measuring the components of the second extraction residual liquid, and returning the second extraction residual liquid to a lithium precipitation workshop, wherein the measurement results are shown in table 2. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step five: carrying out countercurrent washing on the rubidium-loaded organic phase by using distilled water for 5min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing solution, and returning the second washing solution to a lithium precipitation workshop;
carrying out back extraction on the washed loaded rubidium organic phase by using sulfuric acid with the concentration of 98% as back extraction acid, wherein the back extraction time is 5min, the phase ratio of the back extraction organic phase to water is 15:1, obtaining a rubidium salt back extraction solution and a second blank organic phase, measuring the components of the rubidium salt back extraction solution, and recycling the second blank organic phase, wherein the measurement results are shown in table 2;
the cesium salt stripping solution is concentrated until crystals are precipitated, and after cooling to 25 ℃, solid-liquid separation is performed to obtain a rubidium salt and a second filtrate, the rubidium salt is dried to obtain a rubidium sulfate product, the components of the dried rubidium salt are measured, and the measurement results are shown in table 3, and it can be seen from table 3 that the content of the rubidium sulfate product in the obtained rubidium salt exceeds 99% by the above method.
TABLE 2
TABLE 3
As described above, according to the above method and the measurement results in tables 2 and 3, it is understood that: acidifying the lithium precipitation mother liquor acid to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH value meets the requirement, and enriching rubidium and cesium in the lithium precipitation mother liquor to obtain a rubidium and cesium salt solution; and sequentially obtaining cesium salt of a cesium sulfate product with the content exceeding 99% and rubidium salt of a rubidium sulfate product with the content exceeding 99% through extraction separation and back extraction crystallization separation twice. The method simplifies the process flow, realizes the environmental protection requirement of zero discharge of wastewater, and obviously improves the recovery rate of the rubidium and cesium salt, so that the recovery rate of the rubidium and cesium salt in the extraction solid phase exceeds 99 percent.
Example 2
The method comprises the following steps: weighing 1.0L of lepidolite lithium precipitation mother liquor in a reaction kettle, adding nitric acid into the reaction kettle, wherein the addition amount is suitable for measuring the pH value of the lithium precipitation mother liquor in the reaction kettle to be 1-4, so as to obtain an acidizing solution;
adding flaky sodium hydroxide into the acidizing fluid in the reaction kettle, wherein the addition amount is preferably measured to obtain that the pH value of the lithium precipitation mother liquor in the reaction kettle is 8-10, so as to obtain alkalizing fluid;
concentrating the alkalized solution by adopting a concentration separation technology, carrying out solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, and recycling the first potassium sodium salt for use in lepidolite roasting ingredients;
after the concentrated solution is subjected to temperature reduction treatment, solid-liquid separation is performed to obtain a rubidium-cesium salt solution and a second potassium sodium salt, the components of the rubidium-cesium salt solution are measured, the measurement results are shown in table 4, and the second potassium sodium salt is recycled and used for lepidolite roasting ingredients.
Step two: placing the separated rubidium-cesium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured that the pH value of lithium precipitation mother liquor in a reaction kettle is 10-12, adding a first organic solvent with the volume ratio of an extracting agent to a diluting agent being 2:1 into the extraction tank to carry out countercurrent extraction treatment on the rubidium-cesium salt solution, wherein the extraction time is 5min, the ratio of an extraction organic phase to an extraction aqueous phase is 2:1, obtaining a rubidium salt solution loaded with a cesium organic phase and a first extraction residual liquid, measuring the components of the rubidium salt solution, and measuring the measurement results are shown in table 4. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step three: carrying out countercurrent washing on the cesium-loaded organic phase by using distilled water for 5min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
the cesium salt stripping solution and a first blank organic phase are obtained by performing stripping on the washed cesium-loaded organic phase by using nitric acid as stripping acid, wherein the stripping time is 5min, and the phase ratio of the stripping organic phase to water is 15:1, the components of the cesium salt stripping solution are determined, the determination results are shown in table 4, and the first blank organic phase is recycled;
and (3) concentrating the cesium salt stripping solution until crystals are separated out, cooling to 25 ℃, performing solid-liquid separation to obtain cesium salt and a first filtrate, drying the cesium salt to obtain a cesium sulfate product, measuring the components of the dried cesium salt, and determining the measurement result as shown in table 5, wherein the content of the cesium nitrate product in the obtained cesium salt is more than 99% by the method shown in table 5.
Step four: placing the separated rubidium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of lithium precipitation mother liquor in a reaction kettle to be 12-14, adding a second organic solvent with the volume ratio of an extracting agent to a diluting agent being 3:2 into the extraction tank to perform extraction treatment on the rubidium-cesium salt solution, extracting for 5min, obtaining a rubidium-loaded organic phase and a second extraction residual liquid with the extraction organic phase and water phase ratio being 5:1, measuring the components of the second extraction residual liquid, and returning the second extraction residual liquid to a lithium precipitation workshop, wherein the measurement results are shown in table 4. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step five: carrying out countercurrent washing on the rubidium-loaded organic phase by using distilled water for 5min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing solution, and returning the second washing solution to a lithium precipitation workshop;
carrying out back extraction on the washed loaded rubidium organic phase by using nitric acid as a back extraction acid, wherein the back extraction time is 5min, the phase ratio of the back extraction organic phase to water is 15:1, obtaining a rubidium salt back extraction solution and a second blank organic phase, measuring the components of the rubidium salt back extraction solution, and recycling the second blank organic phase, wherein the measurement results are shown in a table 4;
the cesium salt back extraction solution is concentrated until crystals are precipitated, and is cooled to 25 ℃ to be subjected to solid-liquid separation to obtain a rubidium salt and a second filtrate, the rubidium salt is dried to obtain a rubidium sulfate product, the components of the dried rubidium salt are measured, and the measurement results are shown in table 5, and it is understood from table 5 that the content of the rubidium nitrate-containing product in the obtained rubidium salt exceeds 99% by the above method.
TABLE 4
TABLE 5
As described above, according to the above method and the measurement results in tables 4 and 5, it is understood that: acidifying the lithium precipitation mother liquor to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH meets the requirement, and enriching rubidium and cesium in the lithium precipitation mother liquor to obtain a rubidium and cesium salt solution; and sequentially obtaining cesium salt of a cesium nitrate product with the content exceeding 99% and rubidium salt of a rubidium nitrate product with the content exceeding 99% through extraction separation and back extraction crystallization separation twice. The method simplifies the process flow, realizes the environmental protection requirement of zero discharge of wastewater, and obviously improves the recovery rate of the rubidium and cesium salt, so that the recovery rate of the rubidium and cesium salt in the extraction solid phase exceeds 99 percent.
Example 3
The method comprises the following steps: weighing 1.0L of lepidolite lithium precipitation mother liquor in a reaction kettle, adding sulfuric acid with the concentration of 98% into the reaction kettle, and preferably measuring the pH value of the lithium precipitation mother liquor in the reaction kettle to be 1-4 so as to obtain an acidizing solution;
adding liquid sodium hydroxide into the acidizing fluid in the reaction kettle, wherein the addition amount is preferably measured to obtain that the pH value of the lithium precipitation mother liquor in the reaction kettle is 8-10, so as to obtain alkalizing fluid;
concentrating the alkalized solution by adopting a concentration separation technology, carrying out solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, and recycling the first potassium sodium salt for use in lepidolite roasting ingredients;
after the concentrated solution is subjected to temperature reduction treatment, solid-liquid separation is performed to obtain a rubidium-cesium salt solution and a second potassium sodium salt, the components of the rubidium-cesium salt solution are measured, the measurement results are shown in table 6, and the second potassium sodium salt is recycled and used for lepidolite roasting ingredients.
Step two: placing the separated rubidium-cesium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of lithium precipitation mother liquor in a reaction kettle to be 10-12, adding a first organic solvent with the volume ratio of an extracting agent to a diluting agent being 2:1 into the extraction tank to perform countercurrent extraction treatment on the rubidium-cesium salt solution, extracting for 3min, comparing an extraction organic phase with water to be 1:1, obtaining a rubidium salt solution loaded with a cesium organic phase and a first extraction residual liquid, measuring the components of the rubidium salt solution, and measuring the measurement results to be shown in table 6. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step three: carrying out countercurrent washing on the cesium-loaded organic phase by using distilled water for 3min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
back-extracting the washed cesium-loaded organic phase by using sulfuric acid with the concentration of 98% as back-extraction acid, wherein the back-extraction time is 3min, the phase ratio of the back-extraction organic phase to water is 15:1, obtaining a cesium salt back-extraction solution and a first blank organic phase, measuring the components of the cesium salt back-extraction solution, and recycling the first blank organic phase, wherein the measurement results are shown in table 6;
the cesium salt back-extraction solution is concentrated until crystals are separated out, solid-liquid separation is carried out after the crystals are cooled to 35 ℃, cesium salt and first filtrate are obtained, cesium salt is dried to obtain cesium sulfate products, components of the dried cesium salt are measured, measurement results are shown in table 7, and it can be seen from table 7 that the content of cesium sulfate-containing products in the obtained cesium salt is more than 99% by the method.
Step four: placing the separated rubidium salt solution into an extraction tank, adding sheet sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of a lithium precipitation mother solution in a reaction kettle to be 12-14, adding a second organic solvent with the volume ratio of an extracting agent to a diluting agent being 3:2 into the extraction tank to perform extraction treatment on the rubidium-cesium salt solution, extracting for 3min, comparing an extraction organic phase with water being 1:1, obtaining a rubidium-loaded organic phase and a second extraction residual liquid, measuring the components of the second extraction residual liquid, and returning the second extraction residual liquid to a lithium precipitation workshop, wherein the measurement results are shown in table 2. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step five: carrying out countercurrent washing on the rubidium-loaded organic phase by using distilled water for 3min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing solution, and returning the second washing solution to a lithium precipitation workshop;
carrying out back extraction on the washed loaded rubidium organic phase by using sulfuric acid with the concentration of 98% as back extraction acid, wherein the back extraction time is 3min, the ratio of the back extraction organic phase to water is 15:1, obtaining a rubidium salt back extraction solution and a second blank organic phase, measuring the components of the rubidium salt back extraction solution, and recycling the second blank organic phase, wherein the measurement results are shown in table 6;
the cesium salt back-extraction solution is concentrated until crystals are precipitated, and after cooling to 35 ℃, solid-liquid separation is performed to obtain a rubidium salt and a second filtrate, the rubidium salt is dried to obtain a rubidium sulfate product, the components of the dried rubidium salt are measured, and the measurement results are shown in table 7, and it is understood from table 7 that the content of the rubidium sulfate-containing product in the obtained rubidium salt by the above method exceeds 99%.
TABLE 6
TABLE 7
As described above, the following methods, as well as the measurement results in tables 2 and 3, show that: acidifying the lithium precipitation mother liquor to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH meets the requirement, and enriching rubidium and cesium in the lithium precipitation mother liquor to obtain a rubidium and cesium salt solution; and sequentially obtaining the cesium salt of the cesium sulfate product with the content exceeding 99 percent and the rubidium salt of the rubidium sulfate product with the content exceeding 99 percent through two times of extraction separation and back extraction crystallization separation. The method simplifies the process flow, realizes the environmental protection requirement of zero discharge of wastewater, and obviously improves the recovery rate of the rubidium and cesium salt, so that the recovery rate of the rubidium and cesium salt in the extraction solid phase exceeds 99 percent.
Example 4
The method comprises the following steps: weighing 1.0L of lepidolite lithium precipitation mother liquor in a reaction kettle, adding nitric acid into the reaction kettle, wherein the adding amount is suitable for measuring the pH value of the lithium precipitation mother liquor in the reaction kettle to be 1-4 so as to obtain acidizing fluid;
adding sheet sodium hydroxide into the acidizing fluid in the reaction kettle, wherein the addition amount is preferably measured to ensure that the pH value of the lithium precipitation mother liquor in the reaction kettle is 8-10, so as to obtain alkalizing fluid;
concentrating the alkalized solution by adopting a concentration separation technology, carrying out solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, and recycling the first potassium sodium salt for use in lepidolite roasting ingredients;
after the concentrated solution is subjected to cooling treatment, a rubidium-cesium salt solution and a second potassium sodium salt are obtained through solid-liquid separation, the components of the rubidium-cesium salt solution are measured, the measurement results are shown in table 8, and the second potassium sodium salt is recycled and can be used for lepidolite roasting batching.
Step two: placing the separated rubidium-cesium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured that the pH value of a lithium precipitation mother liquor in a reaction kettle is 10-12, adding a first organic solvent with the volume ratio of an extracting agent to a diluting agent being 2:1 into the extraction tank to perform countercurrent extraction treatment on the rubidium-cesium salt solution, extracting for 4min, and measuring the components of the rubidium salt solution, wherein the ratio of an extraction organic phase to a water phase is 1.5:1, so that a rubidium-salt solution loaded with cesium organic phase and a primary extraction residual liquid is obtained, and the measurement results are shown in a table 8. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step three: carrying out countercurrent washing on the cesium-loaded organic phase by using distilled water for 4min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
the cesium salt stripping solution and a first blank organic phase are obtained by performing stripping on the washed cesium-loaded organic phase by using nitric acid as stripping acid, wherein the stripping time is 4min, and the phase ratio of the stripping organic phase to water is 15:1, the components of the cesium salt stripping solution are determined, the determination results are shown in table 8, and the first blank organic phase is recycled;
and (3) concentrating the cesium salt stripping solution until crystals are separated out, cooling to 30 ℃, performing solid-liquid separation to obtain cesium salt and a first filtrate, drying the cesium salt to obtain a cesium sulfate product, and measuring the components of the dried cesium salt, wherein the measurement results are shown in table 9, and it can be known from table 9 that the content of the cesium nitrate-containing product in the obtained cesium salt is more than 99% by the method.
Step four: placing the separated rubidium salt solution into an extraction tank, adding flaky sodium hydroxide, wherein the adding amount is preferably measured to obtain the pH value of lithium precipitation mother liquor in a reaction kettle to be 12-14, adding a second organic solvent with the volume ratio of an extracting agent to a diluting agent being 3:2 into the extraction tank to perform extraction treatment on the rubidium-cesium salt solution, extracting for 4min, obtaining a rubidium-loaded organic phase and a second extraction raffinate with the extraction organic phase and water phase ratio being 2.5:1, measuring the components of the second extraction raffinate, and returning the second extraction raffinate to a lithium precipitation workshop, wherein the measurement results are shown in table 8. Wherein the extractant consists of t-BAMBP and sulfonated kerosene in a volume ratio of 2: 1.
Step five: carrying out countercurrent washing on the rubidium-loaded organic phase by using distilled water for 4min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing solution, and returning the second washing solution to a lithium precipitation workshop;
carrying out back extraction on the washed loaded rubidium organic phase by using nitric acid as a back extraction acid, wherein the back extraction time is 4min, the phase ratio of the back extraction organic phase to water is 15:1, obtaining a rubidium salt back extraction solution and a second blank organic phase, measuring the components of the rubidium salt back extraction solution, and recycling the second blank organic phase, wherein the measurement results are shown in a table 8;
the cesium salt back extraction solution was concentrated until crystals precipitated, cooled to 30 ℃, and subjected to solid-liquid separation to obtain a rubidium salt and a second filtrate, the rubidium salt was dried to obtain a rubidium sulfate product, the components of the dried rubidium salt were measured, and the measurement results are shown in table 9, and it is understood from table 9 that the content of the rubidium nitrate-containing product in the obtained rubidium salt exceeds 99% by the above-described method.
TABLE 8
TABLE 9
As described above, according to the above method and the measurement results in tables 4 and 5, it is understood that: acidifying the lithium precipitation mother liquor to remove carbonate in the liquor, then carrying out alkalization treatment, concentrating and filtering to remove most of potassium and sodium salts after the pH meets the requirement, and enriching rubidium and cesium in the lithium precipitation mother liquor to obtain a rubidium and cesium salt solution; and sequentially obtaining cesium salt of a cesium nitrate product with the content exceeding 99% and rubidium salt of a rubidium nitrate product with the content exceeding 99% through extraction separation and back extraction crystallization separation twice. The method simplifies the process flow, realizes the environmental protection requirement of zero discharge of wastewater, and obviously improves the recovery rate of the rubidium and cesium salt, so that the recovery rate of the rubidium and cesium salt in the extraction solid phase exceeds 99 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for separating and extracting rubidium and cesium salt from lepidolite lithium precipitation mother liquor is characterized by comprising the following steps:
1) acidifying lepidolite lithium precipitation mother liquor to obtain an acidified solution, adding alkali into the acidified solution to adjust the acidified solution to obtain an alkalized solution with the pH value of 8-10, concentrating the alkalized solution, performing solid-liquid separation to obtain a concentrated solution and a first potassium sodium salt, cooling the concentrated solution, and performing solid-liquid separation to obtain a rubidium-cesium salt solution and a second potassium sodium salt; wherein, the first potassium sodium salt and the second potassium sodium salt can be used for lepidolite roasting ingredients;
2) adding alkali into a rubidium-cesium salt solution to adjust the pH value to 10-12, and performing primary extraction and separation to obtain a rubidium salt solution loaded with a cesium organic phase and a primary extraction residual liquid;
3) carrying out first washing, back extraction and crystallization separation treatment on the cesium-loaded organic phase to obtain cesium salt;
4) adding alkali into the rubidium salt solution to adjust the pH value to 12-14, carrying out secondary extraction and separation to obtain a rubidium-loaded organic phase and a secondary extraction residual liquid, and returning the secondary extraction residual liquid to a lithium precipitation workshop;
5) and carrying out secondary washing, back extraction and crystallization separation treatment on the loaded rubidium organic phase to obtain rubidium salt.
2. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the acidizing solution in the step 1) is obtained by adding sulfuric acid with a preset concentration into the lepidolite lithium precipitation mother liquor, and the pH value is 1-4.
3. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the first extraction is an extraction treatment with a first organic solvent, the extraction time is 3-5 min, and the ratio of an extraction organic phase to water is (1-2): 1; the first organic solvent is composed of an extracting agent and a diluent, and the volume ratio of the extracting agent to the diluent is 2: 1.
4. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the specific steps of the first washing, back extraction and crystallization separation treatment comprise:
washing treatment: washing the cesium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed cesium-loaded organic phase and a first washing liquid, and returning the first washing liquid to a lithium precipitation workshop;
back extraction treatment: carrying out back extraction on the washed cesium-loaded organic phase by using sulfuric acid or nitric acid as back extraction acid, wherein the back extraction time is 3-5 min, and the ratio of the back extraction organic phase to water is 15: 1; obtaining cesium salt stripping solution and a first blank organic phase, wherein the first blank organic phase is recycled;
crystallization and separation: and concentrating the cesium salt back extraction solution until crystals are separated out, cooling to 25-35 ℃, performing solid-liquid separation to obtain cesium salt and a first filtrate, and drying the cesium salt to obtain a cesium sulfate product or a cesium nitrate product.
5. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the second extraction is an extraction treatment with a second organic solvent, the extraction time is 3-5 min, and the ratio of an extraction organic phase to water is (1-5): 1; the first organic solvent consists of an extracting agent and a diluent, and the volume ratio of the extracting agent to the diluent is 3: 2.
6. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to any one of claims 3 or 5, wherein the extracting agent consists of t-BAMBP and sulfonated kerosene.
7. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 6, wherein the volume ratio of t-BAMBP to sulfonated kerosene is 2: 1.
8. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the specific steps of the second washing, back extraction and crystallization separation treatment comprise:
washing treatment: washing the rubidium-loaded organic phase by using distilled water for 3-5 min, wherein the ratio of the organic phase to water is 10:1, so as to obtain a washed rubidium-loaded organic phase and a second washing solution, and returning the second washing solution to a lithium precipitation workshop;
back extraction treatment: carrying out back extraction on the washed rubidium-loaded organic phase by using sulfuric acid or nitric acid as back extraction acid, wherein the back extraction time is 3-5 min, and the ratio of the back extraction organic phase to water is 15: 1; obtaining a rubidium salt stripping solution and a second blank organic phase, wherein the second blank organic phase is recycled;
and (3) crystallization separation: and concentrating the rubidium salt stripping solution until crystals are precipitated, cooling to 25-35 ℃, performing solid-liquid separation to obtain a rubidium salt and a second filtrate, drying the rubidium salt to obtain a rubidium sulfate product or a rubidium nitrate product, and returning the second filtrate to a lithium precipitation workshop.
9. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the alkali adding adjustment treatment in the step 2) and the step 7) is alkalization treatment by adding flaky sodium hydroxide.
10. The method for separating and extracting rubidium and cesium salts from lepidolite lithium precipitation mother liquor according to claim 1, wherein the alkalization solution is obtained by adding flake sodium hydroxide or liquid sodium hydroxide into the acidified lepidolite lithium precipitation mother liquor.
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| CN117051260A (en) * | 2023-08-16 | 2023-11-14 | 徐浩 | Treatment process of lithium-containing multi-metal solution |
| CN118561302A (en) * | 2024-07-31 | 2024-08-30 | 江西金德锂新能源科技有限公司 | Automatic control method for rubidium carbonate production line |
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