CN114635047A - Method for extracting cesium in salt lake brine - Google Patents
Method for extracting cesium in salt lake brine Download PDFInfo
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- CN114635047A CN114635047A CN202210355264.3A CN202210355264A CN114635047A CN 114635047 A CN114635047 A CN 114635047A CN 202210355264 A CN202210355264 A CN 202210355264A CN 114635047 A CN114635047 A CN 114635047A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for extracting cesium in salt lake brine, which comprises the following steps: (1) adjusting the pH value of the salt lake brine, mixing the salt lake brine with the extraction organic phase for extraction, and separating to obtain a cesium-loaded organic phase; (2) and (3) carrying out back extraction on the mixed stripping agent and the cesium-loaded organic phase obtained in the step (1), and standing to obtain cesium-loaded stripping solution. The method for extracting cesium from salt lake brine provided by the invention can realize high-efficiency separation of impurity elements such as cesium and K, Rb, the total yield of cesium is more than 65%, the extraction method has the advantages of large treatment capacity, simple process and equipment, small investment and easiness in realization of continuous production.
Description
Technical Field
The invention relates to the field of hydrometallurgy, relates to a method for extracting and recovering cesium, and particularly relates to a method for extracting cesium in salt lake brine.
Background
Cesium is an extremely important rare precious metal resource and has great significance in economy and strategy. It has better ductility, good electric and thermal conductivity, stronger chemical activity and excellent photoelectric effect performance, and is a high-performance industrial metal. Cesium is used in photovoltaic cells, photomultiplier tubes, infrared spectrometers, catalysts for various organic reactions, scintillation counters, and magnetohydrodynamic power generation, among others. In addition, cesium plays an important role in high-tech fields such as fission products, ion rockets, atomic clocks and the like, and belongs to a three-element resource required by the development of high and new technology industries.
The salt lake brine contains abundant cesium resources, but the concentration is generally low and is generally within 10mg/L, and the cesium content in part of the salt lake brine and the lithium extraction mother liquor can reach 2-100mg/L or even higher. However, the other metal elements, such as sodium and potassium, coexisting in the brine are high, and can reach several grams or even tens of grams, which makes the extraction of cesium in the brine of the salt lake very difficult due to the alkali metal ions. In the process of extracting potassium chloride and other salts in a salt lake, cesium salt is entrained and separated out, and in addition, huge energy waste is caused along with the outflow of geothermal water containing abundant cesium resources. Therefore, how to find an effective separation means has become a hot spot of current research on efficiently extracting cesium resources in the production process of salt lake brine salt products.
Among the separation methods, the extraction method has the advantages of simple and convenient operation, easy serialization, large treatment capacity and the like, and is most widely applied. The extracting agents commonly used for cesium are substituted phenols and calixarene crown ethers. The substituted phenol reagent is generally applied to the extraction of alkali metal ions in a strong alkaline solution; calixarene crown ether reagents are generally applied to recovery of cesium in strongly acidic nuclear waste liquid. The operating conditions of the strong acid and the strong base are not suitable for a near-neutral salt lake system, so that a milder neutral or near-neutral extraction technology needs to be developed to realize the extraction of the salt lake cesium resource.
CN 107460344A discloses a method for extracting rubidium and cesium in salt lake brine, which comprises the following steps: (1) mixing t-BAMBP and a diluent to obtain an organic phase, then adding an alkaline solution and the organic phase to carry out saponification reaction, and layering to obtain a saponified organic phase and an alkali liquor; (2) extracting the saponified organic phase-to-salt lake brine obtained in the step (1) to obtain an organic extract phase and a water system raffinate phase; (3) and (3) mixing the organic extraction phase obtained in the step (2) with a stripping agent for stripping to obtain a stripping phase containing Cs (I) and Rb (I) and a blank organic phase. The method adopts the mode of alkali washing and saponifying the organic phase for extraction, does not need to add strong alkaline substances into salt lake brine to adjust the pH value, has low alkali liquid consumption, can be recycled, avoids the environment pollution caused by the generation of a large amount of waste alkali liquid, and is suitable for a neutral or weak alkaline salt lake brine system. However, the lye used in the alkaline washing saponification will be lost due to the emulsification during the extraction process.
CN 107254589A discloses a method for separating and extracting rubidium and cesium in salt lake brine by a t-BAMBP extraction method, wherein the t-BABP is used as an extraction agent, and the rubidium and cesium in the salt lake brine are extracted and separated in a box-type countercurrent mode; the method comprises the following steps: A. detecting the ion concentration; B. an acidification section: taking t-BAMBP as an extraction phase, and carrying out countercurrent acidification on the extraction phase and a mixed acid solution in a box-type extraction tank; C. an extraction section: carrying out countercurrent extraction on the acidified extraction phase and salt lake brine containing rubidium and cesium in a box-type extraction tank; D. a washing section: carrying out reverse-phase washing on the extracted rubidium-cesium solution; E. a stripping section: carrying out reverse phase back extraction on the washed extraction phase; F. and (4) carrying out reverse phase washing and impurity removal on the extracted extract phase, discharging the obtained effluent liquid as waste, and recycling the effluent extract phase. The recovery method has complex flow and is not beneficial to industrial production.
In summary, how to develop a near-neutral system salt lake cesium resource extraction and separation process with large processing capacity, short flow and easy industrialization is a problem which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for extracting cesium in salt lake brine. The method provided by the invention can realize the high-efficiency separation of impurity elements such as cesium and K, Rb, the total yield of cesium is more than 70%, the extraction method has the advantages of large treatment capacity, simple process and equipment, small investment and easy realization of continuous production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for extracting cesium in salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine, mixing the salt lake brine with the extraction organic phase for extraction, and separating to obtain a cesium-loaded organic phase;
(2) and (3) carrying out back extraction on the mixed stripping agent and the cesium-loaded organic phase obtained in the step (1), and standing to obtain cesium-loaded stripping solution.
The method comprises the steps of mixing a composite extracting agent and a diluent to obtain an organic phase, adjusting the pH value of a water phase, mixing the two phases to extract cesium, and separating to obtain a cesium loaded organic phase; and (4) carrying out back extraction and separation on the obtained cesium-loaded organic phase to obtain cesium-loaded back extraction solution. The method provided by the invention can realize the high-efficiency separation of impurity elements such as cesium and K, Rb, the total yield of cesium is more than 65%, the extraction method has the advantages of large treatment capacity, simple process and equipment, small investment and easy realization of continuous production.
The salt lake brine provided by the invention can be all types of cesium-containing brine, including salt field old brine, raw brine, intercrystalline brine, geothermal water and the like. Wherein the cesium concentration is any concentration, and the plasma concentration of potassium, rubidium, calcium, magnesium is 0 to saturation.
Preferably, the adjusted end point of step (1) is that the salt lake brine has a ph value of 10-13, for example, 10, 10.5, 11, 11.5, 12, 12.5 or 13, but not limited to the recited values, and other values not recited in the range of values are also applicable.
The pH value of the salt lake brine is adjusted by adopting an alkaline solution, wherein the alkaline solution comprises a sodium hydroxide solution.
Preferably, the organic phase of step (1) comprises a complex extractant and diluent.
Preferably, the concentration of the complex extractant in the organic phase of the extraction is in the range of 40 to 330mmol/L, for example 40mmol/L, 50mmol/L, 70mmol/L, 100mmol/L, 150mmol/L, 200mmol/L, 250mmol/L, 300mmol/L or 330mmol/L, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the composite extractant comprises a crown ether extractant and a phenol alcohol extractant.
The composite extracting agent provided by the invention can avoid the harsh conditions of strong acid or strong base which are needed when the extracting agent is used independently.
Preferably, the volume ratio of the crown ether-based extractant to the phenol alcohol-based extractant is 1 (3-30), and may be, for example, 1:3, 1:5, 1:7, 1:9, 1:11, 1:13, 1:15, 1:17, 1:19, 1:21, 1:23, 1:25, 1:27, or 1:30, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the crown ether-based extractant includes any one of calix [4] -crown-6, calix [4] -crown-6 derivatives, 21-crown-7 or 21-crown-7 derivatives or a combination of at least two thereof, typical but not limiting combinations include a combination of [4] -crown-6 and calix [4] -crown-6 derivatives, a combination of calix [4] -crown-6 derivatives and 21-crown-7, a combination of calix [4] -crown-6, calix [4] -crown-6 derivatives and 21-crown-7, a combination of calix [4] -crown-6 derivatives, 21-crown-7 and 21-crown-7 derivatives, or a combination of calix [4] -crown-6, calix [4] -crown-6 derivatives, a combination of calix [4] -crown-7 derivatives, a combination of at least two thereof, A combination of 21-crown-7 and 21-crown-7 derivatives.
Exemplary, inventive cup [4]]The crown-6 derivatives comprise different alkyl groups attached to the benzene ring of the calixarene, such as methyl, ethyl, n-C3H7、i-C3H7、n-C8H17、CO2C2H5And the like.
The 21-crown-7 derivatives of the invention include benzo-21-crown-7, dibenzo-21-crown-7 and the like.
Preferably, the phenolic alcohol extractant comprises any one or a combination of at least two of 2- (. alpha. -methylbenzyl) phenol, 4-methyl-2- (. alpha. -methylbenzyl) phenol, 4-ethyl-2- (. alpha. -methylbenzyl) phenol, 4-isopropyl-2- (. alpha. -methylbenzyl) phenol, 4-tert-amyl-2- (. alpha. -methylbenzyl) phenol, 4-fluoro-2- (. alpha. -methylbenzyl) phenol, or 2, 4-dimethyl-6- (. alpha. -methylbenzyl) phenol, with typical but non-limiting combinations including a combination of 2- (. alpha. -methylbenzyl) phenol and 4-methyl-2- (. alpha. -methylbenzyl) phenol, and, A combination of 4-methyl-2- (. alpha. -methylbenzyl) phenol and 4-ethyl-2- (. alpha. -methylbenzyl) phenol, a combination of 2- (. alpha. -methylbenzyl) phenol, 4-isopropyl-2- (. alpha. -methylbenzyl) phenol and 4-tert-amyl-2- (. alpha. -methylbenzyl) phenol, a combination of 4-fluoro-2- (. alpha. -methylbenzyl) phenol and 2, 4-dimethyl-6- (. alpha. -methylbenzyl) phenol, or a combination of 2- (. alpha. -methylbenzyl) phenol, 4-methyl-2- (. alpha. -methylbenzyl) phenol, 4-ethyl-2- (. alpha. -methylbenzyl) phenol, 4-isopropyl-2- (. alpha. -methylbenzyl) phenol and 4-tert-amyl-2- (. alpha. -methylbenzyl) phenol -methylbenzyl) phenol combinations.
Preferably, the diluent comprises any one or a combination of at least two of n-hexane, cyclohexane, cyclohexanone, benzene, toluene, xylene, diethylbenzene, nitrobenzene, carbon tetrachloride, chloroform, aviation kerosene, sulfonated kerosene, or petroleum ether, and typical, but non-limiting, combinations include a combination of n-hexane, cyclohexane, and cyclohexanone, a combination of benzene, toluene, xylene, diethylbenzene, and nitrobenzene, a combination of carbon tetrachloride and chloroform, or a combination of aviation kerosene, sulfonated kerosene, and petroleum ether.
Preferably, the extraction temperature in step (1) is 20-30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the extraction time in step (1) is 30-100min, such as 30min, 40min, 50min, 60min, 70min, 80min, 90min or 100min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the volume ratio of the extraction organic phase to the salt lake brine in the extraction in the step (1) is 1 (0.2-5), and for example, the volume ratio can be 1:0.2, 0:0.5, 1:1, 1:2, 1:3, 1:4 or 1:5, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the temperature of the stripping in step (2) is 20-50 ℃, for example, 20 ℃, 24 ℃, 28 ℃, 32 ℃, 36 ℃, 40 ℃, 44 ℃, 48 ℃ or 50 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the stripping time in step (2) is 30-100min, such as 30min, 40min, 50min, 60min, 70min, 80min, 90min or 100min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the volume ratio of the stripping agent to the cesium-loaded organic phase is 1 (1-100), and may be, for example, 1:1, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1: 70. 1:80, 1:90 or 1:100, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
Preferably, the stripping agent comprises water and/or stripping acid.
Preferably, the stripping acid comprises any one of formic acid, acetic acid, hydrochloric acid, nitric acid, hydrobromic acid, carbonic acid or sulfuric acid or a combination of at least two thereof, and typical, but non-limiting, combinations include a combination of formic acid, hydrochloric acid, nitric acid and sulfuric acid, a combination of formic acid, acetic acid, hydrochloric acid and nitric acid, a combination of hydrobromic acid, carbonic acid and sulfuric acid, or a combination of hydrochloric acid, nitric acid, hydrobromic acid and carbonic acid.
Preferably, the concentration of the stripping acid is 0 to 25mmol/L, for example 0mmol/L, 1mmol/L, 5mmol/L, 10mmol/L, 15mmol/L, 20mmol/L or 25mmol/L, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
As a preferred technical scheme, the method for extracting cesium from salt lake brine provided by the invention comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 10-13, mixing the salt lake brine with the extraction organic phase, extracting for 30-100min at the temperature of 20-30 ℃, and separating to obtain a cesium-loaded organic phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1 (0.2-5); the extraction organic phase comprises a composite extracting agent and a diluent, and the concentration of the composite extracting agent in the extraction organic phase is 40-330 mmol/L; the composite extractant comprises crown ether extractants and phenol alcohol extractants, wherein the volume ratio of the crown ether extractants to the phenol alcohol extractants is 1 (3-30);
(2) carrying out back extraction on the mixed back extraction agent and the cesium-loaded organic phase obtained in the step (1) at the temperature of 20-50 ℃ for 30-100min, and standing to obtain cesium-loaded back extraction liquid; the volume ratio of the stripping agent to the cesium loaded organic phase is 1 (1-100).
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for extracting cesium from salt lake brine provided by the invention can realize high-efficiency separation of impurity elements such as cesium and K, Rb, and the total yield of cesium is more than 65%;
(2) the method for extracting cesium from salt lake brine provided by the invention has the advantages of large treatment capacity, simple process and equipment, low investment and easy realization of continuous production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In order to show the extraction effect of the method, the salt lake brine treated by the embodiment of the invention is the same salt lake brine, wherein the initial concentration of cesium is 10 mmol/L.
Example 1
The embodiment provides a method for extracting cesium from salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 12, mixing the salt lake brine with the extraction organic phase, extracting for 50min at the temperature of 25 ℃, and separating to obtain a cesium-loaded organic phase and a raffinate phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1: 1; the extraction organic phase comprises a composite extracting agent and n-hexane, and the concentration of the composite extracting agent in the extraction organic phase is 130 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the volume ratio of the BPC6 to the t-BAMBP is 1: 12;
(2) mixing 10mmol/L hydrochloric acid with the cesium-loaded organic phase obtained in the step (1), performing back extraction for 50min at the temperature of 30 ℃, and standing to obtain cesium-loaded back extraction solution; the volume ratio of the stripping agent to the cesium loaded organic phase is 1: 1.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 81.8% and the recovery rates of Cs (I) and Cs (I) were 65.5%, respectively.
Example 2
The embodiment provides a method for extracting cesium from salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 13, mixing the salt lake brine with the extraction organic phase, extracting for 50min at the temperature of 25 ℃, and separating to obtain a cesium-loaded organic phase and a raffinate phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1: 1; the extraction organic phase comprises a composite extracting agent and nitrobenzene, and the concentration of the composite extracting agent in the extraction organic phase is 170 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the volume ratio of the BPC6 to the t-BAMBP is 1: 16;
(2) mixing 10mmol/L hydrochloric acid with the cesium-loaded organic phase obtained in the step (1), performing back extraction for 50min at the temperature of 30 ℃, and standing to obtain cesium-loaded back extraction solution; the volume ratio of the stripping agent to the cesium loaded organic phase is 1: 1.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 84.7% and the recovery rates of Cs (I) and Cs (I) were 66.8%, respectively.
Example 3
The embodiment provides a method for extracting cesium from salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 10, mixing the salt lake brine with the extraction organic phase, extracting for 50min at the temperature of 25 ℃, and separating to obtain a cesium-loaded organic phase and a raffinate phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1: 1; the extraction organic phase comprises a composite extracting agent and toluene, and the concentration of the composite extracting agent in the extraction organic phase is 210 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the volume ratio of the BPC6 to the t-BAMBP is 1: 20;
(2) back extraction is carried out on 10mmol/L sulfuric acid and the cesium loaded organic phase obtained in the step (1) for 50min at the temperature of 30 ℃, and cesium loaded back extraction liquid is obtained after standing; the volume ratio of the stripping agent to the cesium loaded organic phase is 1: 1.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 86.8% and the recovery rates of Cs (I) and Cs (I) were 68.5%, respectively.
Example 4
The embodiment provides a method for extracting cesium from salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 12, mixing the salt lake brine with the extraction organic phase, extracting for 50min at the temperature of 25 ℃, and separating to obtain a cesium-loaded organic phase and a raffinate phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1: 1; the extraction organic phase comprises a composite extracting agent and aviation kerosene, and the concentration of the composite extracting agent in the extraction organic phase is 250 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the volume ratio of the BPC6 to the t-BAMBP is 1: 24;
(2) mixing 10mmol/L hydrochloric acid with the cesium-loaded organic phase obtained in the step (1), performing back extraction for 50min at the temperature of 30 ℃, and standing to obtain cesium-loaded back extraction solution; the volume ratio of the stripping agent to the cesium loaded organic phase is 1: 1.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 87.7% and 69.2%, respectively.
Example 5
The embodiment provides a method for extracting cesium from salt lake brine, which comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 12, mixing the salt lake brine with the extraction organic phase, extracting for 50min at the temperature of 25 ℃, and separating to obtain a cesium-loaded organic phase and a raffinate phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1: 1; the extraction organic phase comprises a composite extracting agent and nitrobenzene, and the concentration of the composite extracting agent in the extraction organic phase is 290 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the volume ratio of BPC6 to t-BAMBP is 1: 28;
(2) mixing 10mmol/L hydrochloric acid with the cesium-loaded organic phase obtained in the step (1), performing back extraction for 50min at the temperature of 30 ℃, and standing to obtain cesium-loaded back extraction solution; the volume ratio of the stripping agent to the cesium loaded organic phase is 1: 1.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rate of Cs (I) was 88.8%, and the recovery rate of Cs (I) was 70.1%.
Example 6
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: in this example, 10mmol/L hydrochloric acid in step (3) was changed to water, and the stripping temperature was changed to 40 ℃.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 88.8% and the recovery rate of Cs (I) was 72.2%, respectively.
Example 7
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: this example changed the organic phase from the extraction described in step (2) to t-BAMBP at a concentration of 280mmol/L and nitrobenzene.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the cs (i) extraction rate was 9.3%, and the recovery rate of cs (i) was 6.2%.
Example 8
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: this example changed the organic phase from step (2) to BPC6 and nitrobenzene, the concentration of BPC6 was 10 mmol/L.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 4.1% and the recovery rate of Cs (I) was 2.2%, respectively.
Example 9
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: in the embodiment, the volume ratio of the extraction organic phase in the extraction in the step (2) to the salt lake brine is changed to 1: 0.2.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 94.8% and the recovery rate of Cs (I) was 77.2%, respectively.
Example 10
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: in the embodiment, the volume ratio of the extraction organic phase in the extraction in the step (2) to the salt lake brine is changed to 1:5, and the concentration of the composite extracting agent in the extraction organic phase is 330 mmol/L; the composite extractant comprises BPC6 and t-BAMBP, and the concentration ratio of BPC6 to t-BAMBP is 5: 28.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rate of Cs (I) was 93.2%, and the recovery rate of Cs (I) was 76.3%.
Example 11
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: in the embodiment, the volume ratio of the stripping agent to the cesium-loaded organic phase in the step (3) is changed to 1:10, and the concentration of the stripping agent is 20 mmol/L.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 88.8% and the recovery rate of Cs (I) was 65.4%, respectively.
Example 12
This example provides a method for extracting cesium from salt lake brine, which only differs from example 5 in that: in the embodiment, the volume ratio of the stripping agent to the cesium-loaded organic phase in the step (3) is changed to 1:100, and the concentration of the stripping agent is 25 mmol/L.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 88.8% and the recovery rate of Cs (I) was 50.1%, respectively.
Example 13
This example provides a method for extracting cesium from salt lake brine, which only differs from example 5 in that: in the embodiment, the concentration of the hydrochloric acid in the step (3) is changed to 25 mmol/L.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rate of Cs (I) was 88.8%, and the recovery rate of Cs (I) was 65.1%.
Example 14
This example provides a method for extracting cesium from salt lake brine, which differs from example 5 only in that: in the embodiment, the concentration of the hydrochloric acid in the step (3) is changed to 30 mmol/L.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 88.8% and the recovery rate of Cs (I) was 51.4%, respectively.
Comparative example 1
This comparative example provides a method of extracting cesium from salt lake brine that differs from example 5 only in that: the comparative example omits the adjustment of the pH value of the salt lake brine, and the pH value of the salt lake brine is 8.5.
The ion concentrations of the aqueous raffinate phase and the cesium-loaded strip liquor were tested by inductively coupled plasma atomic emission spectroscopy and the results showed: the extraction rates of Cs (I) and Cs (I) were 2.8% and the recovery rates of Cs (I) and Cs (I) were 2.1%, respectively.
In summary, the method for extracting cesium from salt lake brine provided by the invention mixes the composite extracting agent and the diluent to obtain an organic phase, adjusts the pH value of the aqueous phase, mixes the two phases to extract cesium, and separates the cesium to obtain a cesium loaded organic phase; and (4) carrying out back extraction and separation on the obtained cesium-loaded organic phase to obtain cesium-loaded back extraction solution. The method provided by the invention can realize the high-efficiency separation of impurity elements such as cesium and K, Rb, the total yield of cesium is more than 65%, the extraction method has the advantages of large treatment capacity, simple process and equipment, small investment and easy realization of continuous production.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for extracting cesium from salt lake brine is characterized by comprising the following steps:
(1) adjusting the pH value of the salt lake brine, mixing the salt lake brine with the extraction organic phase for extraction, and separating to obtain a cesium-loaded organic phase;
(2) and (2) carrying out back extraction on the mixed back extraction agent and the cesium-loaded organic phase obtained in the step (1), and standing to obtain cesium-loaded back extraction solution.
2. The method for extracting cesium from salt lake brine according to claim 1, wherein the end point of the adjustment in step (1) is the pH value of salt lake brine is 10-13.
3. The method for extracting cesium from salt lake brine according to claim 1 or 2, characterized in that said extracting organic phase of step (1) comprises a complex extractant and diluent;
preferably, the concentration of the composite extracting agent in the extraction organic phase is 40-330 mmol/L.
4. The method for extracting cesium from salt lake brine according to claim 3, wherein said complex extractant comprises crown ether type extractants and phenol alcohol type extractants;
preferably, the volume ratio of the crown ether extractant to the phenol alcohol extractant is 1 (3-30).
5. The method for extracting cesium from salt lake brine according to claim 4, wherein said crown ether type extractant comprises any one of calix [4] -crown-6, calix [4] -crown-6 derivatives, 21-crown-7 or 21-crown-7 derivatives or a combination of at least two thereof;
preferably, the phenolic alcohol extractant includes any one of 2- (α -methylbenzyl) phenol, 4-methyl-2- (α -methylbenzyl) phenol, 4-ethyl-2- (α -methylbenzyl) phenol, 4-isopropyl-2- (α -methylbenzyl) phenol, 4-tert-amyl-2- (α -methylbenzyl) phenol, 4-fluoro-2- (α -methylbenzyl) phenol, or 2, 4-dimethyl-6- (α -methylbenzyl) phenol, or a combination of at least two thereof.
6. The method of claim 3, wherein the diluent comprises any one or a combination of at least two of n-hexane, cyclohexane, cyclohexanone, benzene, toluene, xylene, diethylbenzene, nitrobenzene, carbon tetrachloride, chloroform, aviation kerosene, sulfonated kerosene, or petroleum ether.
7. The method for extracting cesium from salt lake brine according to any one of claims 1 to 6, characterized in that the temperature of the extraction of step (1) is 20 to 30 ℃;
preferably, the extraction time of the step (1) is 30-100 min;
preferably, the volume ratio of the extracted organic phase to the salt lake brine in the extraction in the step (1) is 1 (0.2-5).
8. The method for extracting cesium from salt lake brine according to any one of claims 1 to 7, characterized in that the temperature of back extraction in step (2) is 20 to 50 ℃;
preferably, the time for the back extraction in the step (2) is 30-100 min;
preferably, the volume ratio of the stripping agent to the cesium-loaded organic phase is 1 (1-100).
9. The method for extracting cesium from salt lake brine according to any one of claims 1-8, wherein said stripping agent comprises water and/or stripping acid;
preferably, the stripping acid comprises any one of formic acid, acetic acid, hydrochloric acid, nitric acid, hydrobromic acid, carbonic acid or sulfuric acid or a combination of at least two of the same;
preferably, the concentration of the stripping acid is 0-25 mmol/L.
10. The method for extracting cesium from salt lake brine according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) adjusting the pH value of the salt lake brine to 10-13, mixing the salt lake brine with the extraction organic phase, extracting for 30-100min at the temperature of 20-30 ℃, and separating to obtain a cesium-loaded organic phase; the volume ratio of the extracted organic phase to the salt lake brine in the extraction is 1 (0.2-5); the extraction organic phase comprises a composite extracting agent and a diluent, and the concentration of the composite extracting agent in the extraction organic phase is 40-330 mmol/L; the composite extractant comprises a crown ether extractant and a phenol alcohol extractant, and the volume ratio of the crown ether extractant to the phenol alcohol extractant is 1 (3-30);
(2) carrying out back extraction on the mixed back extraction agent and the cesium-loaded organic phase obtained in the step (1) at the temperature of 20-50 ℃ for 30-100min, and standing to obtain cesium-loaded back extraction liquid; the volume ratio of the stripping agent to the cesium loaded organic phase is 1 (1-100).
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