CN114672654B - Method for recycling rubidium and cesium in salt lake brine by using heteropolyacid salt electrode - Google Patents
Method for recycling rubidium and cesium in salt lake brine by using heteropolyacid salt electrode Download PDFInfo
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Abstract
The invention relates to a method for recovering rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, which comprises the following steps: (1) Placing the heteropolyacid salt electrode in salt lake brine, and applying a reduction potential to obtain the heteropolyacid salt electrode loaded with alkali metal ions; (2) Placing the heteropolyacid salt electrode loaded with the alkali metal ions in the step (1) into a regeneration liquid, and applying oxidation potential to release the alkali metal ions; the heteropolyacid salt electrode in the step (1) contains a vanadium source; the valence state of vanadium in the vanadium source is +5. The heteropolyacid salt electrode regulates and controls the valence state change of the self central element by using potential so as to capture and release alkali metal ions, and other chemical reagents are not needed to be added in the regeneration process, so that harmless recovery of rubidium cesium resources in salt lake brine is realized; the heteropolyacid salt electrode has low preparation cost, high ion exchange capacity, low energy consumption in the process of recovering metal ions and no secondary pollution.
Description
Technical Field
The invention belongs to the field of separation and recovery of valuable metals in salt lake brine, and particularly relates to a method for recovering rubidium and cesium in salt lake brine by using a heteropolyacid salt electrode.
Background
Along with the gradual expansion of the application of rubidium and cesium in various fields such as catalysts, biological medicines, high-precision-point scientific and technological products and the like, the gradual failure of rubidium and cesium ore resources, people aim at the salt lake resources with huge rubidium and cesium reserves. Meanwhile, serious environmental pollution is caused by leaching rubidium and cesium ions from ores, and calcination and leaching links are avoided by extracting rubidium and cesium resources from salt lakes, so that the method is an environment-friendly extraction means. Therefore, the extraction of rubidium cesium resources from salt lakes is significant.
At present, rubidium cesium ion separation technology comprises a chemical precipitation method, an adsorption method, an ion exchange method, a floatation method, a solvent extraction method and the like. CN106552602B discloses a preparation method of a composite adsorption material for adsorbing rubidium cesium ions, the preparation method comprises: preparing a polymer layer containing catechol structure by in-situ polymerization on the surface of a porous material, and then growing an ion exchange functional nano adsorbent layer on the surface of the polymer layer in-situ to obtain the composite adsorption material; the porous material is a membrane or a resin or a sponge or silica gel or alumina or diatomaceous earth; the polymer layer containing catechol structure is polydopamine or caffeic acid or catechin; the ion exchange functional adsorbent is a transition metal ferrous or ferric oxide or hydrated phosphocomplex or heteropolyacid salt. The composite adsorption material has strong capability of complexing and adsorbing rubidium and cesium, and can be used for adsorbing rubidium and cesium in salt lake brine. However, the preparation method is complex and has high cost.
CN107460344B discloses a method for extracting rubidium and cesium from salt lake brine, which comprises the following steps: mixing t-BAMBP and a diluent to obtain an organic phase, adding an alkaline solution and the organic phase to carry out saponification reaction, and layering to obtain a saponified organic phase and alkali liquor; extracting the saponified organic relative salt lake brine to obtain an organic extraction phase and a water system raffinate phase; and carrying out back extraction on the obtained organic extract phase to obtain a back extraction phase containing Cs (I) and Rb (I) and a blank organic phase. The method does not need to add strong alkaline substances into the salt lake brine to adjust the pH, realizes the efficient extraction of Cs (I) and Rb (I) in the salt lake brine system, and is suitable for the salt lake brine system which is neutral or weak alkaline. However, the method needs an organic solvent, and secondary pollution is easy to cause.
CN110293004a discloses a precipitation flotation separation system for rubidium and cesium in an aqueous solution, the precipitation flotation separation system comprising: a precipitant comprising at least phosphomolybdate; and a collector and a frother comprising at least a cationic surfactant. The flotation separation method comprises the following steps: adding a precipitant, a collector and a foaming agent into an aqueous solution containing cesium ions for reaction to precipitate cesium ions, and collecting precipitate solids obtained by the reaction through flotation separation treatment. By combining the precipitation and floatation processes, a precipitation floatation system using the aluminophosphate as a precipitator is provided, and is used for separating and extracting rubidium and brilliant resources, so that the problems of dissolution loss of a supported ammonium aluminophosphate adsorbent or complex preparation of materials and the like are avoided. But the sedimentation-flotation process is time consuming.
Therefore, a method for extracting rubidium and cesium resources from salt lakes, which has high recovery rate, no secondary pollution and repeated material utilization, is needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for recycling rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, which has the advantages of low cost, high ion exchange capacity, low energy consumption in the process of recycling alkali metal ions and no secondary pollution.
In order to achieve the technical effects, the invention adopts the following technical scheme:
the invention provides a method for recycling rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, which comprises the following steps:
(1) Placing the heteropolyacid salt electrode in salt lake brine, and applying a reduction potential to obtain the heteropolyacid salt electrode loaded with alkali metal ions;
(2) Placing the heteropolyacid salt electrode loaded with the alkali metal ions in the step (1) into a regeneration liquid, and applying oxidation potential to release the alkali metal ions;
the heteropolyacid salt electrode in the step (1) contains a vanadium source;
the valence state of vanadium in the vanadium source is +5.
The heteropolyacid salt electrode and the counter electrode are immersed into salt lake brine to form a loop, a reduction potential is applied to the heteropolyacid salt electrode, the electronegativity of the heteropolyacid salt electrode shows affinity with alkali metal ions, and the heteropolyacid salt electrode is captured; immersing the heteropolyacid salt electrode and the counter electrode loaded with alkali metal ions into the regeneration liquid to form a loop, applying oxidation potential to the heteropolyacid salt electrode, oxidizing the heteropolyacid salt electrode, displaying positive electricity, releasing the alkali metal ions into the regeneration liquid, and regenerating and recovering the electrode.
According to the invention, the heteropolyacid salt electrode regulates and controls the valence state change of the self central element by using the potential, so that the capture and release of alkali metal ions are realized, no other chemical reagent is needed to be added in the regeneration process, no secondary pollution is generated, and the harmless recovery of rubidium cesium resources in salt lake brine is realized.
In the invention, the heteropolyacid salt electrode can be repeatedly utilized for a plurality of times, has good stability, is not easy to damage the structure, and can still realize the efficient capturing and releasing of alkali metal ions after the heteropolyacid salt electrode is repeatedly used for a plurality of times.
In the present invention, the counter electrode comprises a graphite electrode.
As a preferred technical scheme of the invention, the preparation method of the heteropolyacid salt electrode in the step (1) comprises the following steps: and mixing the heteropoly acid salt molecular sieve with an adhesive and a solvent, and coating the obtained slurry on a conductive substrate to obtain the heteropoly acid salt electrode.
Preferably, the mass ratio of the heteropolyacid salt molecular sieve to the binder is (6-10): 1, for example, may be 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10:1, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, polyvinylidene fluoride or polytetrafluoroethylene, typical but non-limiting examples of which are: a combination of polyvinylidene fluoride and polyvinylidene fluoride, a combination of polyvinylidene fluoride and polytetrafluoroethylene, or a combination of polyvinylidene fluoride, polyvinylidene fluoride and polytetrafluoroethylene, etc.
Preferably, the conductive substrate comprises any one of carbon cloth, foam nickel, titanium plate, copper plate, platinum sheet, conductive carbon material, and typical but non-limiting examples of the combination are: a combination of carbon cloth and foam nickel, a combination of a titanium plate and a copper plate, or a combination of a platinum sheet and carbon cloth, etc.
In the present invention, the solvent includes dimethylformamide.
As a preferred technical scheme of the invention, the preparation method of the heteropolyacid salt molecular sieve comprises the following steps: mixing a vanadium source, a silicon source, an alkaline substance, a reducing agent, sodium salt and a solvent, aging, and performing hydrothermal reaction to obtain the heteropolyacid salt molecular sieve.
Preferably, the vanadium source comprises any one or a combination of at least two of sodium metavanadate, vanadium pentoxide or ammonium metavanadate, typical but non-limiting examples of such combinations being: a combination of carbon cloth and foam nickel, a combination of a titanium plate and a copper plate, or a combination of a platinum sheet and carbon cloth, etc.
Preferably, the silicon source comprises any one or a combination of at least two of sodium silicate, sodium silicate nonahydrate, or silicon dioxide, typical but non-limiting examples of which are: a combination of sodium silicate and silica, a combination of sodium silicate nonahydrate and silica, or a combination of sodium silicate, sodium silicate nonahydrate and silica, or the like.
Preferably, the alkaline substance comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the reducing agent comprises any one or a combination of at least two of oxalic acid, oxalic acid dihydrate, formic acid or citric acid, typical but non-limiting examples of which are: a combination of oxalic acid and formic acid, a combination of formic acid and citric acid, or a combination of sodium silicate, oxalic acid dihydrate, formic acid and citric acid, and the like.
Preferably, the mass ratio of the vanadium source to the silicon source is 1: (5-20), for example, may be 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20, etc., but are not limited to the recited values, as are other non-recited values within the range of values.
Preferably, the mass ratio of the vanadium source to the reducing agent is 1: (2-6), for example, may be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, or 1:6, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the heteropolyacid salt molecular sieve has strong capability of capturing alkali metal ions, good treatment capability and high regeneration efficiency, and can effectively separate and recycle rubidium cesium valuable ion resources in salt lake brine.
In a preferred embodiment of the present invention, the aging time is 12-48h, for example, 12h, 14h, 18h, 20h, 24h, 28h, 30h, 34h, 38h, 40h, 44h or 48h, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The temperature of the hydrothermal reaction is preferably 180 to 230 ℃, and may be 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃ or the like, for example, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are equally applicable.
Preferably, the hydrothermal reaction time is 24-72h, for example, 24h, 28h, 30h, 34h, 38h, 40h, 44h, 48h, 50h, 54h, 58h, 60h, 64h, 68h, 70h or 72h, etc., but not limited to the recited values, other non-recited values in the numerical range are equally applicable.
As a preferable technical scheme of the invention, the salt lake brine in the step (1) contains rubidium and/or cesium.
Preferably, the alkali metal ion of step (1) comprises Rb + And/or Cs + 。
As a preferred embodiment of the present invention, the reduction potential in the step (1) is-3 to 0V and does not include 0V, and may be, for example, -3V, -2.8V, -2.6V, -2.4V, -2.2V, -2V, -1.8V, -1.6V, -1.4V, -1.2V, -1V, -0.8V, -0.6V, -0.4V, -0.2V or-0.1V, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the present invention, the reduction electrochemical treatment time in the step (1) is 30 to 120min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, etc., but the present invention is not limited to the recited values, and other non-recited values in the numerical range are applicable.
As a preferable technical scheme of the invention, the regenerating liquid in the step (2) comprises any one of sodium chloride, sodium sulfate or sodium nitrate.
In a preferred embodiment of the present invention, the concentration of the regenerating liquid in the step (2) is 0.001 to 0.1mol/L, for example, 0.001mol/L, 0.003mol/L, 0.005mol/L, 0.007mol/L, 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.07mol/L, 0.09mol/L or 0.1mol/L, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In a preferred embodiment of the present invention, the oxidation potential in step (2) is 0 to 3V, and not 0V is included, and may be, for example, 0.2V, 0.4V, 0.6V, 0.8V, 1V, 1.2V, 1.4V, 1.6V, 1.8V, 2V, 2.2V, 2.4V, 2.6V, 2.8V or 3V, etc., but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the present invention, the time of the oxidation electrochemical treatment in the step (2) is 30 to 120min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, etc., but the present invention is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In the invention, the heteropolyacid salt electrode is V at the reduction potential 5+ Reduction to V 4+ Electronegativity, in order to achieve charge balance, alkali metal ions are trapped in the material and then V at oxidation potential 4+ Oxidation to V 5+ The positive electricity is developed, and the positive electricity is repelled with alkali metal ions, and the alkali metal ions are released into the regeneration liquid. The valence state adjustable mechanism greatly strengthens the capability of the electroactive ion exchange functional material for capturing and releasing metal ions.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Placing a heteropolyacid salt electrode in salt lake brine containing rubidium and/or cesium, and applying a reduction potential to obtain a load Rb + And/or Cs + The reduction potential is-3 to 0V, and does not include 0V;
(2) Loading Rb of step (1) + And/or Cs + The heteropolyacid salt electrode is placed in 0.001-0.1mol/L regeneration liquid, and oxidation potential is applied to realize Rb + And/or Cs + The oxidation potential is 0 to 3V, and does not include 0V;
the heteropolyacid salt electrode in the step (1) contains a vanadium source;
the valence state of vanadium in the vanadium source is +5.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the heteropolyacid salt electrode, the valence state change of the central element is regulated and controlled by the potential, so that the capture and release of alkali metal ions are realized, no other chemical reagent is needed to be added in the regeneration process, secondary pollution is avoided, and the harmless recovery of rubidium and cesium resources in salt lake brine is realized;
(2) The invention combines the advantages of potential difference as driving force with the characteristic of variable valence state of vanadium element when separating and recovering rubidium and cesium ions by using the electric control ion exchange technology, thereby greatly improving the separation and recovery efficiency of rubidium and cesium ions;
(3) The heteropolyacid salt molecular sieve has strong capturing capability of rubidium and cesium ions, good treatment capability and high regeneration efficiency, and can effectively separate and recycle rubidium and cesium resources in salt lake brine;
(4) The voltage applied by the method is far smaller than the voltage standard of industrial electricity, and the energy consumption and the cost of the whole treatment process are low.
Drawings
FIG. 1 is an electron microscopic view of sodium vanadium silicate prepared in example 1 of the present invention;
fig. 2 is a graph showing the time-dependent cesium ion content of the sodium vanadium silicate electrode when a reduction voltage and an oxidation voltage are applied to the sodium vanadium silicate electrode for capturing and releasing cesium ions in example 4.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a heteropoly acid salt molecular sieve and a heteropoly acid salt electrode thereof, wherein the preparation method of the heteropoly acid salt molecular sieve comprises the following steps: 28.47g of sodium silicate nonahydrate, 8.02g of sodium chloride, 3.016g of sodium hydroxide and 65mL of deionized water are mixed to obtain a mixed solution A; 9.45g of oxalic acid and 25ml of deionized water are mixed, and then 1.83g of sodium metavanadate is added to obtain a mixed solution B; adding the mixed solution B into the mixed solution A, mixing and stirring for 1h, aging for 24h, performing hydrothermal reaction at 180 ℃ for 36h, filtering, washing and drying to obtain the sodium vanadium silicate.
The preparation method of the heteropolyacid salt electrode comprises the following steps: mixing sodium vanadate silicate, polyvinylidene fluoride and dimethylformamide under stirring, wherein the mass ratio of the sodium vanadate silicate to the polyvinylidene fluoride is 1: and 0.125, coating the obtained slurry on the surface of carbon cloth, and drying to obtain the vanadium sodium silicate electrode.
Example 2
The embodiment provides a preparation method of a heteropoly acid salt molecular sieve and a heteropoly acid salt electrode thereof, wherein the preparation method of the heteropoly acid salt molecular sieve comprises the following steps: 28.47g of sodium silicate nonahydrate, 8.02g of sodium chloride, 3.016g of sodium hydroxide and 65mL of deionized water are mixed to obtain a mixed solution A; 9.45g of oxalic acid and 25ml of deionized water are mixed, and then 1.75g of sodium metavanadate is added to obtain a mixed solution B; adding the mixed solution B into the mixed solution A, mixing and stirring for 1h, ageing for 4h, performing hydrothermal reaction at 230 ℃ for 24h, filtering, washing and drying to obtain the sodium vanadium silicate.
The preparation method of the heteropolyacid salt electrode comprises the following steps: mixing sodium vanadate silicate, polyvinylidene fluoride and dimethylformamide under stirring, wherein the mass ratio of the sodium vanadate silicate to the polyvinylidene fluoride is 1: and 0.1, coating the obtained slurry on the surface of foam nickel, and drying to obtain the vanadium sodium silicate electrode.
Example 3
The embodiment provides a preparation method of a heteropoly acid salt molecular sieve and a heteropoly acid salt electrode thereof, wherein the preparation method of the heteropoly acid salt molecular sieve comprises the following steps: 28.47g of sodium silicate nonahydrate, 8.02g of sodium chloride, 3.016g of sodium hydroxide and 65mL of deionized water are mixed to obtain a mixed solution A; 9.45g of oxalic acid and 25ml of deionized water are mixed, and then 2.73g of vanadium pentoxide is added to obtain a mixed solution B; adding the mixed solution B into the mixed solution A, mixing and stirring for 1h, aging for 30h, performing hydrothermal reaction at 200 ℃ for 30h, filtering, washing and drying to obtain the sodium vanadium silicate.
The preparation method of the heteropolyacid salt electrode comprises the following steps: mixing sodium vanadate silicate, polyvinylidene fluoride and dimethylformamide under stirring, wherein the mass ratio of the sodium vanadate silicate to the polyvinylidene fluoride is 1: and 0.15, coating the obtained slurry on the surface of carbon cloth, and drying to obtain the vanadium sodium silicate electrode.
Example 4
The embodiment provides a method for recovering rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, wherein the heteropoly acid salt electrode adopts the sodium vanadium silicate electrode prepared in the embodiment 1, and the method comprises the following steps:
(1) The salt lake brine comprises the following components: 50mg/L Cs + The sodium vanadium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the counter electrode is placed in salt lake brine to form a closed loop, and the closed loop is subjected to electrochemical treatment for 80min by applying-3.0V voltage to obtain a load Cs + Sodium vanadium silicate electrode;
(2) Loading Cs by step (1) + The vanadium sodium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the counter electrode is placed in 0.001mol/L sodium chloride solution to form a closed loop, 3.0V voltage is applied to carry out electrochemical treatment for 80min, and Cs are captured + The vanadium sodium silicate electrode is regenerated to realize Cs + Is released.
Example 5
The embodiment provides a method for recovering rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, wherein the heteropoly acid salt electrode adopts the sodium vanadium silicate electrode prepared in the embodiment 1, and the method comprises the following steps:
(1) The salt lake brine comprises the following components: 50mg/L Cs + And 50mg/LRb + The sodium vanadium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the counter electrode is placed in salt lake brine to form a closed loop, and the closed loop is subjected to electrochemical treatment for 80min by applying a voltage of-1.0V to obtain a load Cs + And Rb + Sodium vanadium silicate electrode;
(2) Loading Cs by step (1) + And Rb + The vanadium sodium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the counter electrode is placed in 0.005mol/L sodium chloride solution to form a closed loop, and the electrochemical treatment is carried out for 80min by applying 1.0V voltage to capture Cs + And Rb + The vanadium sodium silicate electrode is regenerated to realize Cs + And Rb + Is released.
Example 6
The embodiment provides a method for recovering rubidium and cesium in salt lake brine by using a heteropoly acid salt electrode, wherein the heteropoly acid salt electrode adopts the sodium vanadium silicate electrode prepared in the embodiment 1, and the method comprises the following steps:
(1) The salt lake brine comprises the following components: 50mg/L Cs + And 50mg/L Rb + The sodium vanadium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, and the counter electrode is placed in salt lake brineA closed loop is formed in the process, and a voltage of-0.3V is applied to perform electrochemical treatment for 80min to obtain a load Cs + And Rb + Sodium vanadium silicate electrode;
(2) Loading Cs by step (1) + And Rb + The vanadium sodium silicate electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the counter electrode is placed in 0.005mol/L sodium chloride solution to form a closed loop, and the electrochemical treatment is carried out for 80min by applying 0.3V voltage to capture Cs + And Rb + The vanadium sodium silicate electrode is regenerated to realize Cs + And Rb + Is released.
Example 7
This example differs from example 4 only in that the conditions were the same as in example 4 except that the heteropolyacid salt electrode was a sodium vanadate-silicate electrode prepared in example 2.
Example 8
This example differs from example 4 only in that the conditions were the same as in example 4 except that the heteropolyacid salt electrode was a sodium vanadate-silicate electrode prepared in example 3.
Example 9
This example differs from example 4 only in that the conditions were the same as in example 4 except that the heteropolyacid salt electrode was a sodium vanadate electrode obtained by repeating the reduction-oxidation electrochemical treatment 5 times in example 4.
Example 10
This example differs from example 4 only in that the conditions are the same as example 4 except that the applied voltage in step (1) is-4.0V.
Example 11
This example differs from example 4 only in that the conditions are the same as example 4 except that the applied voltage in step (2) is 4.0V.
Example 12
This example differs from example 11 only in that the conditions were the same as in example 11 except that the heteropolyacid salt electrode was a sodium vanadate electrode obtained by repeating the reduction-oxidation electrochemical treatment for 5 times in example 11.
Example 13
The present example differs from example 4 only in that the conditions were the same as example 4 except that the electrochemical treatment time in step (1) was 20 min.
Example 14
The difference between this example and example 4 is that the conditions are the same as example 4 except that the electrochemical treatment time in step (1) is 130 min.
Example 15
The present example differs from example 4 only in that the conditions were the same as example 4 except that the electrochemical treatment time in step (2) was 20 min.
Example 16
The difference between this example and example 4 is that the conditions are the same as example 4 except that the electrochemical treatment time in step (2) is 130 min.
Comparative example 1
The present comparative example differs from example 4 only in that the conditions were the same as example 4 except that the "sodium vanadate-silicate electrode" was replaced with a "Prussian blue electrode".
Comparative example 2
The present comparative example differs from comparative example 1 only in that the conditions were the same as comparative example 1 except that the electrode was a Prussian blue electrode obtained by repeating the reduction-oxidation electrochemical treatment 5 times with comparative example 1.
As can be seen from fig. 1, the sodium vanadium silicate prepared in example 1 of the present invention has a layered structure.
Examples 4-16 and comparative examples 1-2 Cs described in step (1) + And/or Rb + The loading of (2) the Cs + And/or Rb + The regeneration rates of (2) are shown in table 1, wherein a graph of the cesium ion content of the sodium vanadate electrode with time when cesium ions are trapped and released by applying a reduction voltage and an oxidation voltage to the sodium vanadate electrode in example 4 is shown in fig. 2.
TABLE 1
From table 1, the following points can be found:
(1) The method for recovering rubidium and cesium in salt lake brine by using the heteropoly acid salt electrode can realize capturing and releasing of rubidium and cesium in salt lake brine, and the heteropoly acid salt electrode can be repeatedly used for a plurality of times;
(2) As is clear from comparison of example 4 and example 7, when the aging time during the preparation of the heteropolyacid salt molecular sieve is too short, the capability of capturing cesium is lowered due to incomplete formation of crystal nuclei;
(3) As is clear from comparison of example 4 and example 10, when the applied reduction voltage in step (1) is too low, irreversible structural change is generated by the material, resulting in a decrease in the cesium capturing ability thereof;
(4) As can be seen from a comparison of example 4 and examples 11-12, when the applied oxidation voltage in step (2) is too high, irreversible structural changes are generated by the material, which can completely release cesium, but the subsequent adsorption amount is reduced;
(5) As is clear from comparison of examples 4 and examples 13 to 14, when the reduction electrochemical time in the step (1) is too low, the amount of vanadium ions of low valence is small, resulting in a decrease in the cesium capturing ability thereof; when the reduction electrochemical time in the step (1) is too long, the capacity for capturing cesium is the same as that of example 4, but the cost is increased;
(6) As is clear from comparison of examples 4 and examples 15 to 16, when the oxidation electrochemical time in the step (2) is too low, the amount of vanadium ions which are high in valence is small, resulting in a decrease in the release ability of cesium; when the oxidizing electrochemical time in step (2) is too high, the release capacity of cesium is the same as in example 4, but the cost is increased;
(7) As is clear from comparison of example 4 and comparative examples 1 to 2, when the sodium vanadate electrode is replaced with the prussian blue electrode, the adsorption amount is low and the recycling performance is poor due to the poor structural stability of the prussian blue.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (15)
1. A method for recovering rubidium and cesium from salt lake brine by using a heteropolyacid salt electrode, which is characterized by comprising the following steps:
(1) Placing the heteropolyacid salt electrode in salt lake brine, and applying a reduction potential to obtain the heteropolyacid salt electrode loaded with alkali metal ions;
(2) Placing the heteropolyacid salt electrode loaded with the alkali metal ions in the step (1) into a regeneration liquid, and applying oxidation potential to release the alkali metal ions;
the heteropolyacid salt electrode in the step (1) contains a vanadium source;
the valence state of vanadium in the vanadium source is +5;
the preparation method of the heteropolyacid salt electrode in the step (1) comprises the following steps: mixing a heteropoly acid molecular sieve with an adhesive and a solvent, and coating the obtained slurry on a conductive substrate to obtain the heteropoly acid electrode;
the mass ratio of the heteropolyacid salt molecular sieve to the adhesive is (6-10): 1, a step of;
the preparation method of the heteropolyacid salt molecular sieve comprises the following steps: mixing a vanadium source, a silicon source, an alkaline substance, a reducing agent, sodium salt and a solvent, aging, and performing hydrothermal reaction to obtain the heteropolyacid salt molecular sieve;
the vanadium source comprises any one or a combination of at least two of sodium metavanadate, vanadium pentoxide or ammonium metavanadate;
the silicon source comprises any one or at least two of sodium silicate, sodium silicate nonahydrate or silicon dioxide;
the mass ratio of the vanadium source to the silicon source is 1: (5-20);
the mass ratio of the vanadium source to the reducing agent is 1: (2-6).
2. The method of claim 1, wherein the adhesive comprises any one or a combination of at least two of polyvinylidene fluoride, or polytetrafluoroethylene.
3. The method of claim 1, wherein the conductive substrate comprises any one of carbon cloth, nickel foam, titanium plate, copper plate, platinum sheet, conductive carbon material.
4. The method according to claim 1, wherein the alkaline substance comprises sodium hydroxide and/or potassium hydroxide.
5. The method of claim 1, wherein the reducing agent comprises any one or a combination of at least two of oxalic acid, oxalic acid dihydrate, formic acid, or citric acid.
6. The method of claim 1, wherein the aging is for a period of 12-48 hours.
7. The method of claim 1, wherein the temperature of the hydrothermal reaction is 180-230 ℃.
8. The method of claim 1, wherein the hydrothermal reaction is for a period of 24-72 hours.
9. The method of claim 1, wherein the salt lake brine of step (1) comprises rubidium and/or cesium.
10. The method of claim 1, wherein the alkali metal ions of step (1) comprise Rb + And/or Cs + 。
11. The method of claim 1, wherein the reduction potential of step (1) is-3 to 0V and does not include 0V.
12. The method of claim 1, wherein the regeneration liquid of step (2) comprises any one of sodium chloride, sodium sulfate, or sodium nitrate.
13. The method according to claim 1, wherein the concentration of the regenerating liquid in the step (2) is 0.001-0.1mol/L.
14. The method of claim 1, wherein the oxidation potential of step (2) is 0 to 3V and does not include 0V.
15. The method according to claim 1, characterized in that it comprises the steps of:
(1) Placing a heteropolyacid salt electrode in salt lake brine containing rubidium and/or cesium, and applying a reduction potential to obtain a load Rb + And/or Cs + The reduction potential is-3 to 0V, and does not include 0V;
(2) Loading Rb of step (1) + And/or Cs + The heteropolyacid salt electrode is placed in 0.001-0.1mol/L regeneration liquid, and oxidation potential is applied to realize Rb + And/or Cs + The oxidation potential is 0 to 3V, and does not include 0V;
the heteropolyacid salt electrode in the step (1) contains a vanadium source;
the valence state of vanadium in the vanadium source is +5;
the preparation method of the heteropolyacid salt electrode in the step (1) comprises the following steps: mixing a heteropoly acid molecular sieve with an adhesive and a solvent, and coating the obtained slurry on a conductive substrate to obtain the heteropoly acid electrode;
the mass ratio of the heteropolyacid salt molecular sieve to the adhesive is (6-10): 1, a step of;
the preparation method of the heteropolyacid salt molecular sieve comprises the following steps: mixing a vanadium source, a silicon source, an alkaline substance, a reducing agent, sodium salt and a solvent, aging, and performing hydrothermal reaction to obtain the heteropolyacid salt molecular sieve;
the vanadium source comprises any one or a combination of at least two of sodium metavanadate, vanadium pentoxide or ammonium metavanadate;
the silicon source comprises any one or at least two of sodium silicate, sodium silicate nonahydrate or silicon dioxide;
the mass ratio of the vanadium source to the silicon source is 1: (5-20);
the mass ratio of the vanadium source to the reducing agent is 1: (2-6).
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