CN114350950A - Method for extracting rubidium and cesium from complex underground brine - Google Patents
Method for extracting rubidium and cesium from complex underground brine Download PDFInfo
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- CN114350950A CN114350950A CN202110474179.4A CN202110474179A CN114350950A CN 114350950 A CN114350950 A CN 114350950A CN 202110474179 A CN202110474179 A CN 202110474179A CN 114350950 A CN114350950 A CN 114350950A
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- rubidium
- cesium
- brine
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- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 153
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 143
- 239000012267 brine Substances 0.000 title claims abstract description 141
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 141
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000001376 precipitating effect Effects 0.000 claims abstract description 40
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 18
- 239000011591 potassium Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 121
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 103
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 88
- 239000002244 precipitate Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 238000001914 filtration Methods 0.000 claims description 51
- 238000001704 evaporation Methods 0.000 claims description 45
- -1 cesium ions Chemical class 0.000 claims description 43
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 40
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 39
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- FAWNVSNJFDIJRM-UHFFFAOYSA-N [Rb].[Cs] Chemical compound [Rb].[Cs] FAWNVSNJFDIJRM-UHFFFAOYSA-N 0.000 claims description 27
- 230000008020 evaporation Effects 0.000 claims description 26
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 25
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000001103 potassium chloride Substances 0.000 claims description 20
- 235000011164 potassium chloride Nutrition 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 17
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 claims description 17
- 229910001424 calcium ion Inorganic materials 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 14
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 229940102127 rubidium chloride Drugs 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229940071182 stannate Drugs 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000005402 stannate group Chemical group 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- SXKFOROWXJWZAN-UHFFFAOYSA-L rubidium(1+);dichloride Chemical compound [Cl-].[Cl-].[Rb+].[Rb+] SXKFOROWXJWZAN-UHFFFAOYSA-L 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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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 discloses a method for extracting rubidium and cesium from complex underground brine, and solves the problems of high cost and complex process flow of extracting rubidium and cesium from underground brine in the prior art. The invention comprises the following steps of extracting rubidium and cesium from underground brine in sequence: step 1: purifying brine; step 2: rubidium and cesium are primarily enriched; and step 3: rubidium and cesium are deeply enriched; and 4, step 4: precipitating rubidium and cesium; and 5: rubidium and cesium are refined to remove potassium; step 6: extracting cesium; and 7: extracting rubidium; the method has the advantages of effectively extracting rubidium and cesium from underground brine, reducing production cost, avoiding environmental pollution, facilitating operation and the like.
Description
Technical Field
The invention relates to the technical field of bittern chemical industry, in particular to a method for extracting rubidium and cesium from complex underground brine.
Background
Rubidium and cesium are precious rare alkali metals and have very active properties. The abundance of rubidium and cesium in the earth crust is respectively 16 th and 40 th, and due to the wide distribution of rubidium and cesium in the earth crust, separate minerals are rarely formed, and the rubidium and cesium are mainly assigned to solid ores such as lepidolite and caesium stones and brine. Rubidium and cesium exist in minerals mainly in the form of a homomorphic image instead of potassium atoms, and in brine, rubidium and cesium exist together with alkali metal elements with extremely similar properties to potassium, sodium and the like, so that separation and purification of rubidium and cesium are very difficult, and the price of rubidium and cesium is very high. Currently, rubidium salt and cesium salt production in China is mainly produced from recovered mother liquor after lithium is extracted from lepidolite, and the production cost and the yield are low. The content of rubidium and cesium in the brine is high, the storage capacity is large, but the components are complex, so that the brine contains various pliable elements for extracting rubidium and cesium, the engineering application degree of a plurality of single product separation and extraction technologies is not high, and the process is complex.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the present invention provides a method for extracting rubidium and cesium from complex underground brine, which solves the above problems.
A method for extracting rubidium and cesium from complex underground brine is further optimized, and sequentially comprises the following steps:
step 1: purifying brine; removing hydrogen sulfide from underground brine, adding lime slurry to precipitate magnesium ions in the underground brine, filtering and separating, and adding a sodium carbonate solution to precipitate calcium ions in the underground brine to obtain brine A;
step 2: rubidium and cesium are primarily enriched; evaporating and concentrating the brine A, separating out sodium chloride, continuing to concentrate until potassium is saturated, adding water, cooling, separating out potassium chloride, acidifying the potassium separation mother liquor to obtain boric acid, extracting bromine and iodine from the boron extraction mother liquor by adopting an air blowing method to obtain brine B, wherein the concentration of rubidium in the brine B is more than 1g/L, and returning to continue evaporating and concentrating;
and step 3: rubidium and cesium are deeply enriched; when the concentration of lithium ions in the brine B is more than 15g/L, adding a sodium carbonate solution to precipitate the lithium ions after the calcium ions and the magnesium ions are removed; and if the concentration of the lithium ions is less than 15g/L, independently performing evaporation concentration to separate out sodium chloride, cooling to separate out potassium chloride, filtering and separating until the concentration of the lithium ions in the mother liquor is more than 15g/L, precipitating lithium, and returning the mixture of the separated sodium chloride and potassium chloride to the step 2 for evaporation concentration after the mixture is dissolved back in water. Precipitating lithium to obtain brine C, wherein the concentration of rubidium in the brine C is 10-20 g/L, and if the rubidium concentration in the brine C cannot be reached, returning to continue evaporating and concentrating;
and 4, step 4: precipitating rubidium and cesium; adding concentrated hydrochloric acid into the brine C until the hydrogen ion concentration is 0-5 mol/L, adding a stannic chloride solution for precipitation to obtain a rubidium-cesium mixed precipitate A, adding a saturated sodium hydroxide solution into the brine C from which rubidium and cesium are removed, precipitating to obtain stannic hydroxide, and returning the filtered and separated mother liquor to the step 3 for continuous evaporation and concentration;
and 5: rubidium and cesium are refined to remove potassium; adding water into the rubidium-cesium mixed precipitate A obtained in the step 4 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: (1-10), adding a sodium hydroxide solution to adjust the pH value, stirring and reacting, adding concentrated hydrochloric acid, adding a tin chloride solution to precipitate when the hydrogen ion concentration is 0-5 mol/L, and obtaining a rubidium-cesium mixed precipitate B, wherein the concentration of rubidium ions and the concentration of potassium ions in the rubidium-cesium mixed precipitate B are 10-100: 1, if not, returning to the step 5 until the concentration of the precipitate reaches the standard, filtering and separating to obtain a solution D, adding a saturated sodium hydroxide solution into the solution D, precipitating to obtain tin hydroxide, and returning the filtered and separated mother liquor to the step 3 to continue evaporation and concentration;
step 6: extracting cesium; adding water into the rubidium-cesium mixed precipitate B obtained in the step 5 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: (1-10), adding a sodium hydroxide solution until the pH value is 0-7, performing stirring reaction, filtering and separating to obtain a mixed solution of tin hydroxide and rubidium and cesium, performing evaporation concentration on the mixed solution of rubidium and cesium, adding concentrated hydrochloric acid when the concentration of cesium ions in the mixed solution of rubidium and cesium is 10-20 g/L, adding an antimony trichloride solution when the concentration of hydrogen ions is 0-5 mol/L, performing precipitation to obtain cesium chloroantimonate, filtering and separating to obtain a solution E, adding water to the cesium chloroantimonate, and pulping, wherein the mass ratio of the cesium chloroantimonate to the water is 1: (1-10), adding ammonia water to adjust the pH value, precipitating to obtain antimony hydroxide, filtering and separating to obtain filtrate, evaporating to dryness and calcining to obtain crude cesium chloride, and adding water to recrystallize to obtain a cesium chloride product;
and 7: extracting rubidium; adding sodium hydroxide into the solution E for precipitation to obtain antimony hydroxide, adding hydrochloric acid into filtrate obtained by filtering and separating, adding a tin tetrachloride solution for precipitation when the concentration of hydrogen ions is 0-5 mol/L, obtaining rubidium chlorostannate precipitate, continuously adding sodium hydroxide into mother liquor obtained by filtering and separating to obtain solution F and tin hydroxide, returning the solution F to the step 3, adding water into the rubidium chlorostannate precipitate for size mixing, wherein the mass ratio of the rubidium chlorostannate precipitate to the water is 1: (1-10), adding ammonia water until the pH value is 0-7, precipitating to obtain tin hydroxide, filtering and separating to obtain filtrate, evaporating to dryness and calcining to obtain crude rubidium chloride, and adding water to recrystallize to obtain a rubidium chloride product.
Through a method for preferably extracting rubidium and cesium from underground brine, hydrogen sulfide is removed by adopting a blowing-off or oxidation method in a brine purification step, and magnesium ions and calcium ions are removed by a precipitation method, so that the loss of rubidium and cesium forming double salts in a concentration process can be effectively avoided; by adopting a two-stage enrichment process, rubidium and cesium are subjected to primary enrichment under the condition of low concentration, then are subjected to deep enrichment under the condition of high concentration, and mixed salts generated during deep enrichment are redissolved and returned for secondary concentration, so that rubidium and cesium loss caused by a class-quality homography phenomenon is reduced, and rubidium and cesium enrichment efficiency and enrichment yield are improved; the method has the advantages that the precipitation method is adopted to extract and separate the enriched rubidium and cesium from the brine, the precipitator can be recycled repeatedly, toxic substances generated by extraction methods and the like due to the addition of organic solvents are avoided, environmental pollution caused by three-waste discharge is reduced, and the production cost is reduced.
More preferably, the auxiliary materials obtained in the method for extracting rubidium and cesium from the underground brine are recovered, the tin hydroxide precipitated in the step 4, the tin hydroxide separated in the step 6, and the tin hydroxide separated and precipitated in the step 7 are mixed, hydrochloric acid is added to wash the mixture, antimony hydroxide precipitated in the step 6 is added to wash the mixture, and the washed tin hydroxide and antimony hydroxide are dissolved in concentrated hydrochloric acid to prepare tin chloride solution and antimony chloride solution with required concentrations respectively for standby.
Further preferably, the potassium chloride is separated out by cooling in the step 3, wherein the temperature range of cooling is 20-60 ℃. And (3) cooling is adopted to separate out potassium chloride, the cooling temperature range is controlled, the loss rate of the rubidium element can be reduced, high-temperature sodium chloride evaporation is adopted in the step 3, and low-temperature potassium chloride separation is adopted, so that the enrichment concentration of the rubidium element is convenient to improve.
Further preferably, sodium hydroxide solution is added in the step 5 to adjust the pH value, wherein the pH value ranges from 0 to 7. Tin ions in the brine can be precipitated by tin hydroxide through adjusting the pH value, so that sodium, potassium, rubidium and cesium in the chlorine stannate can be released to form an ionic state, the tendency of forming precipitates by potassium and chlorine stannic acid is smaller than that of rubidium and cesium ions, and the concentration of rubidium and potassium in the precipitates is reduced through repeated release and precipitation, so that rubidium and cesium are effectively enriched.
More preferably, ammonia water is added in the step 6 and the step 7 to adjust the pH value, and the pH value ranges from 0 to 7. And (4) by adjusting the pH values in the step (6) and the step (7), the introduction of sodium ions to generate impurities is avoided, and cesium chloride and rubidium chloride can be effectively precipitated.
More preferably, the molar mass of the tin tetrachloride solution added in the step 4 is 120-180% of the molar mass of the rubidium ions and the cesium ions. And 4, in order to precipitate rubidium and cesium, controlling the amount of added stannic chloride to avoid precipitating potassium stannate and sodium stannate.
More preferably, the molar mass of the tin chloride solution added in the step 5 is 10-30% of the molar mass of the rubidium ions and the cesium ions. And (3) carrying out efficient precipitation on the rubidium-cesium mixed precipitate again by controlling the amount of the added tin chloride.
More preferably, the molar mass of the antimony trichloride solution added in the step 6 is 110-130% of that of the cesium ions. By controlling the amount of antimony trichloride solution added, cesium chlorostannate is effectively precipitated.
More preferably, the molar mass of the tin tetrachloride solution added in the step 7 is 110 to 130 percent of the molar mass of the rubidium ions. By controlling the amount of the added tin tetrachloride solution, the rubidium stannate chloride is effectively precipitated.
The invention has the following advantages and beneficial effects:
1. the invention provides a method for extracting rubidium and cesium from complex underground brine, which sequentially comprises brine purification, rubidium and cesium primary enrichment, rubidium and cesium deep enrichment, rubidium and cesium precipitation, rubidium and cesium refining, potassium removal, cesium extraction and rubidium extraction, wherein the rubidium and cesium are extracted and separated from the brine by adopting a precipitation method, a precipitator can be recycled, toxic substances generated by adding an organic solvent in methods such as extraction and the like are avoided, environmental pollution caused by three-waste discharge is reduced, and the production cost is reduced;
2. according to the method, auxiliary materials obtained in the method for extracting rubidium and cesium from underground brine are recovered, the tin hydroxide precipitated in the step 4, the tin hydroxide separated in the step 6 and the tin hydroxide separated and precipitated in the step 7 are mixed, hydrochloric acid is added for washing and then recovering, and the antimony hydroxide precipitated in the step 6 is added with hydrochloric acid for washing and then recovering;
3. cooling to separate out potassium chloride in the step 3, wherein the temperature range of cooling is 20-60 ℃; adding a sodium hydroxide solution to adjust the pH value in the step 5, wherein the pH value ranges from 0 to 7; adding ammonia water in the step 6 and the step 7 to adjust the pH value, wherein the range of the pH value is 0-7; the temperature reduction range is controlled, the loss of rubidium in brine can be reduced, and the pH value is adjusted, so that the rubidium and cesium can be effectively enriched;
4. the molar mass of the tin tetrachloride solution added in the step 4 is 120-180% of that of rubidium ions and cesium ions; the molar mass of the tin chloride solution added in the step 5 is 10-30% of that of rubidium ions and cesium ions; and (3) adding an antimony trichloride solution in the step (6), wherein the molar mass of the antimony trichloride solution is 110% -130% of that of the cesium ions. (ii) a The molar mass of the tin tetrachloride solution added in the step 7 is 110-130% of that of the rubidium ions; the amount of the added solution is respectively controlled, so that the rubidium element and the cesium element in the brine are effectively extracted.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
A method for extracting rubidium and cesium from complex underground brine sequentially comprises the following steps:
step 1: purifying brine; removing hydrogen sulfide from underground brine by adopting a stripping method, adding lime slurry, precipitating magnesium ions in the underground brine when the pH value of the solution is adjusted to be 12, filtering and separating, adding a sodium carbonate solution, wherein the mass of the added sodium carbonate solution is 105% of that of calcium ions in the brine, and precipitating calcium ions in the underground brine to obtain brine A, wherein the concentration of the calcium ions in the brine A is less than 20mg/L, the concentration of the magnesium ions is less than 20mg/L, and the concentration of the hydrogen sulfide is less than 10 g/L;
step 2: rubidium and cesium are primarily enriched; evaporating and concentrating brine A by adopting an MVR hot-pressing salt making method, separating when the concentration of potassium ions in the brine A is 120g/L after sodium chloride is separated out, adding 5% by mass of water, cooling to 30 ℃, separating potassium chloride, adding hydrochloric acid into a potassium separation mother solution, acidifying until the pH value is 2 to obtain boric acid, adding chlorine into a boron extraction mother solution, oxidizing to the potential of 580mv and the potential of 1000mv respectively, and extracting an iodine simple substance and a bromine simple substance in sequence by adopting an air blowing method to obtain brine B, wherein the concentration of rubidium in the brine B is 1.5 g/L;
and step 3: rubidium and cesium are deeply enriched; the concentration of lithium ions in the brine B is 20g/L, after the brine B is heated to 80 ℃, sodium carbonate solution and sodium hydroxide solution are sequentially added, calcium ions and magnesium ions are removed, then sodium carbonate solution is added to precipitate lithium ions, hydrochloric acid is added to adjust the pH value to be 3, the brine B is heated to boil for 10min, then sodium hydroxide solution is added to adjust the pH value to be 8, an MVR hot pressing salt making method is adopted for evaporation and concentration, sodium chloride is separated out, the sodium chloride returns to the step 2 for continuous concentration, the temperature is reduced to be 30 ℃, potassium chloride is separated out after filtration and separation, the potassium chloride returns to the step 2 for continuous evaporation and concentration, brine C is obtained after the step 4 times of cyclic operation, the concentration of rubidium ions in the brine C is 12g/L, and the concentration of cesium ions is 1.5 g/L;
and 4, step 4: precipitating rubidium and cesium; adding concentrated hydrochloric acid into brine C until the hydrogen ion concentration is 2.5mol/L, adding a stannic chloride solution for precipitation, adding the stannic chloride solution with the mass being 120% of that of rubidium and cesium in the brine to obtain a rubidium and cesium mixed precipitate A, adding a saturated sodium hydroxide solution into the brine C from which the rubidium and cesium are removed, precipitating to obtain tin hydroxide when the pH value is adjusted to be 3, continuously adding the sodium hydroxide solution into the filtered and separated mother liquor, adjusting the pH value to be 8, and returning to the step 3 to continuously evaporate and concentrate;
and 5: rubidium and cesium are refined to remove potassium; adding water into the rubidium-cesium mixed precipitate A obtained in the step 4 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: and 3, adding a sodium hydroxide solution to adjust the pH value to 4, stirring and reacting for 2 hours, adding concentrated hydrochloric acid, adding a tin chloride solution to precipitate when the hydrogen ion concentration is 2.5mol/L, wherein the mass of the added tin chloride solution is 20% of that of rubidium and cesium in the brine, obtaining a rubidium and cesium mixed precipitate B, filtering and separating to obtain brine D, returning the brine D to the step 4 to continue precipitating, and circularly operating the step 3 times, wherein the concentration of the rubidium ions and the concentration of the potassium ions in the rubidium and cesium mixed precipitate B are 100: 1;
step 6: extracting cesium; adding water into the rubidium-cesium mixed precipitate B obtained in the step 5 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: adding a sodium hydroxide solution until the pH value is 4, performing a stirring reaction, filtering and separating to obtain a mixed solution of tin hydroxide and rubidium and cesium, performing evaporation concentration on the mixed solution of rubidium and cesium, adding concentrated hydrochloric acid when the concentration of cesium ions in the mixed solution of rubidium and cesium is 10g/L, adding an antimony trichloride solution for precipitation when the concentration of hydrogen ions is 2.5mol/L, adding an antimony trichloride solution to precipitate, wherein the mass of the antimony trichloride solution is 120% of the mass of cesium in brine, obtaining cesium chloroantimonate, filtering and separating to obtain brine E, adding water to the cesium chloroantimonate for size mixing, and the mass ratio of the cesium chloroantimonate to the water is 1: 3, adding ammonia water to adjust the pH value to 3, precipitating to obtain antimony hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude cesium chloride, and adding water to recrystallize for 2 times to obtain a cesium chloride product;
and 7: extracting rubidium; adding sodium hydroxide into brine E to adjust the pH value to 3, precipitating to obtain antimony hydroxide, adding hydrochloric acid into filtrate obtained by filtering and separating, adding a stannic chloride solution to precipitate when the concentration of hydrogen ions is 2.5mol/L, wherein the mass of the added stannic chloride solution is 120% of that of rubidium in brine, obtaining rubidium stannate chloride precipitate, filtering and separating, adding sodium hydroxide to obtain brine F and tin hydroxide, returning the brine F to the step 3, adding water into the rubidium stannate precipitate to mix slurry, and the mass ratio of the rubidium stannate precipitate to water is 1: and 3, adding ammonia water until the pH value is 4, precipitating to obtain tin hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude rubidium chloride, and adding water to recrystallize for 2 times to obtain a rubidium chloride product.
And (2) recovering the auxiliary materials obtained in the step, respectively mixing the tin hydroxide precipitated in the step 4, the tin hydroxide separated in the step 6 and the tin hydroxide separated and precipitated in the step 7, adding hydrochloric acid to perform 4-stage countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: 5, returning to the step 3 after filtration and separation for continuous evaporation and concentration;
and (3) adding hydrochloric acid into the antimony hydroxide precipitated in the step (6) to perform countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: and 5, filtering and separating, returning to the step 3, and continuing to evaporate and concentrate.
Example 2
The embodiment provides a method for extracting rubidium and cesium from complex underground brine, which sequentially comprises the following steps:
step 1: purifying brine; removing hydrogen sulfide from underground brine by adopting a stripping method, adding lime slurry, precipitating magnesium ions in the underground brine when the pH value of the solution is adjusted to be 12, filtering and separating, adding a sodium carbonate solution, wherein the mass of the added sodium carbonate solution is 105% of that of calcium ions in the brine, and precipitating calcium ions in the underground brine to obtain brine A, wherein the concentration of the calcium ions in the brine A is less than 20mg/L, the concentration of the magnesium ions is less than 20mg/L, and the concentration of the hydrogen sulfide is less than 10 g/L;
step 2: rubidium and cesium are primarily enriched; evaporating and concentrating brine A by adopting an MVR hot-pressing salt making method, separating when the concentration of potassium ions in the brine A is 120g/L after sodium chloride is separated out, adding 5% by mass of water, cooling to 30 ℃, separating potassium chloride, adding hydrochloric acid into a potassium separation mother solution, acidifying until the pH value is 2 to obtain boric acid, adding chlorine into a boron extraction mother solution, oxidizing to the potential of 580mv and the potential of 1000mv respectively, and extracting an iodine simple substance and a bromine simple substance in sequence by adopting an air blowing method to obtain brine B, wherein the concentration of rubidium in the brine B is 1.5 g/L;
and step 3: rubidium and cesium are deeply enriched; the concentration of lithium ions in the brine B is 20g/L, after the brine B is heated to 80 ℃, sodium carbonate solution and sodium hydroxide solution are sequentially added, calcium ions and magnesium ions are removed, then sodium carbonate solution is added to precipitate lithium ions, hydrochloric acid is added to adjust the pH value to be 3, the brine B is heated to boil for 10min, then sodium hydroxide solution is added to adjust the pH value to be 8, an MVR hot pressing salt making method is adopted for evaporation and concentration, sodium chloride is separated out, the sodium chloride returns to the step 2 for continuous concentration, the temperature is reduced to be 60 ℃, potassium chloride is separated out after filtration and separation, the potassium chloride returns to the step 2 for continuous evaporation and concentration, brine C is obtained after the step 4 times of cyclic operation, the concentration of rubidium ions in the brine C is 10g/L, and the concentration of cesium ions is 1 g/L;
and 4, step 4: precipitating rubidium and cesium; adding concentrated hydrochloric acid into brine C until the hydrogen ion concentration is 3mol/L, adding a stannic chloride solution for precipitation, adding the stannic chloride solution with the mass being 120% of that of rubidium and cesium in the brine to obtain a rubidium and cesium mixed precipitate A, adding a saturated sodium hydroxide solution into the brine C from which the rubidium and cesium are removed, adjusting the pH value to 4, precipitating to obtain stannic hydroxide, continuously adding the sodium hydroxide solution into the filtered and separated mother liquor, adjusting the pH value to 7, and returning to the step 3 to continue evaporation and concentration;
and 5: rubidium and cesium are refined to remove potassium; adding water into the rubidium-cesium mixed precipitate A obtained in the step 4 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: 10, adding a sodium hydroxide solution to adjust the pH value to 5, stirring and reacting for 2 hours, adding concentrated hydrochloric acid, adding a tin chloride solution to precipitate when the hydrogen ion concentration is 5mol/L, wherein the mass of the added tin chloride solution is 10% of that of rubidium and cesium in brine to obtain a rubidium and cesium mixed precipitate B, filtering and separating to obtain brine D, returning brine E to the step 4 to continue precipitating, and circularly operating the step 3 times, wherein the concentration of rubidium ions and the concentration of potassium ions in the rubidium and cesium mixed precipitate B are 30: 1;
step 6: extracting cesium; adding water into the rubidium-cesium mixed precipitate B obtained in the step 5 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: adding a sodium hydroxide solution until the pH value is 5, performing a stirring reaction, filtering and separating to obtain a mixed solution of tin hydroxide and rubidium and cesium, performing evaporation concentration on the mixed solution of rubidium and cesium until the concentration of cesium ions in the mixed solution of rubidium and cesium is 20g/L, adding concentrated hydrochloric acid, adding an antimony trichloride solution for precipitation when the concentration of hydrogen ions is 5mol/L, adding an antimony trichloride solution with the mass being 110% of the mass of cesium in brine to obtain cesium chloroantimonate, filtering and separating to obtain a solution E, adding water to the cesium chloroantimonate for size mixing, wherein the mass ratio of the cesium chloroantimonate to the water is 1: 10, adding ammonia water to adjust the pH value to 4, precipitating to obtain antimony hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude cesium chloride, and adding water to recrystallize for 2 times to obtain a cesium chloride product;
and 7: extracting rubidium; adding sodium hydroxide into the solution E to adjust the pH value to 5, precipitating to obtain antimony hydroxide, adding hydrochloric acid into filtrate obtained by filtering and separating, adding a tin tetrachloride solution to precipitate when the concentration of hydrogen ions is 5mol/L, adding the tin tetrachloride solution with the mass being 110% of that of rubidium in brine to obtain rubidium stannate chloride precipitate, filtering and separating, adding the sodium hydroxide to obtain a solution F and tin hydroxide, returning the solution F to the step 3, adding water into the rubidium stannate precipitate to prepare slurry, wherein the mass ratio of the rubidium stannate chloride precipitate to the water is 1: and 10, adding ammonia water until the pH value is 5, precipitating to obtain tin hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude rubidium chloride, and adding water to recrystallize for 2 times to obtain a rubidium chloride product.
And (2) recovering the auxiliary materials obtained in the step, respectively mixing the tin hydroxide precipitated in the step 4, the tin hydroxide separated in the step 6 and the tin hydroxide separated and precipitated in the step 7, adding hydrochloric acid to perform 4-stage countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: 5, returning to the step 3 after filtration and separation for continuous evaporation and concentration;
and (3) adding hydrochloric acid into the antimony hydroxide precipitated in the step (6) to perform countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: and 5, filtering and separating, returning to the step 3, and continuing to evaporate and concentrate.
Example 3
The embodiment provides a method for extracting rubidium and cesium from complex underground brine, which sequentially comprises the following steps:
step 1: purifying brine; removing hydrogen sulfide from underground brine by adopting a stripping method, adding lime slurry, precipitating magnesium ions in the underground brine when the pH value of the solution is adjusted to be 12, filtering and separating, adding a sodium carbonate solution, wherein the mass of the added sodium carbonate solution is 105% of that of calcium ions in the brine, and precipitating calcium ions in the underground brine to obtain brine A, wherein the concentration of the calcium ions in the brine A is less than 20mg/L, the concentration of the magnesium ions is less than 20mg/L, and the concentration of the hydrogen sulfide is less than 10 g/L;
step 2: rubidium and cesium are primarily enriched; evaporating and concentrating brine A by adopting an MVR hot-pressing salt making method, separating when the concentration of potassium ions in the brine A is 120g/L after sodium chloride is separated out, adding 5% by mass of water, cooling to 30 ℃, separating potassium chloride, adding hydrochloric acid into a potassium separation mother solution, acidifying until the pH value is 2 to obtain boric acid, adding chlorine into a boron extraction mother solution, oxidizing to the potential of 580mv and the potential of 1000mv respectively, and extracting an iodine simple substance and a bromine simple substance in sequence by adopting an air blowing method to obtain brine B, wherein the concentration of rubidium in the brine B is 1.5 g/L;
and step 3: rubidium and cesium are deeply enriched; the concentration of lithium ions in the brine B is 20g/L, after the brine B is heated to 80 ℃, sodium carbonate solution and sodium hydroxide solution are sequentially added, calcium ions and magnesium ions are removed, then sodium carbonate solution is added to precipitate lithium ions, hydrochloric acid is added to adjust the pH value to be 3, the brine B is heated to boil for 10min, then sodium hydroxide solution is added to adjust the pH value to be 8, an MVR hot pressing salt making method is adopted for evaporation and concentration, sodium chloride is separated out, the sodium chloride returns to the step 2 for continuous concentration, the temperature is reduced to 20 ℃, potassium chloride is separated out after filtration and separation, the potassium chloride returns to the step 2 for continuous evaporation and concentration, brine C is obtained after the step 4 times of cyclic operation, the concentration of rubidium ions in the brine C is 20g/L, and the concentration of cesium ions is 2.5 g/L;
and 4, step 4: precipitating rubidium and cesium; adding concentrated hydrochloric acid into brine C until the hydrogen ion concentration is 2mol/L, adding a stannic chloride solution for precipitation, adding the stannic chloride solution with the mass being 150% of that of rubidium and cesium in the brine to obtain a rubidium and cesium mixed precipitate A, adding a saturated sodium hydroxide solution into the brine C from which the rubidium and cesium are removed, precipitating to obtain tin hydroxide when the pH value is adjusted to 2, continuously adding the sodium hydroxide solution into the filtered and separated mother liquor, adjusting the pH value to 7, and returning to the step 3 to continue evaporation and concentration;
and 5: rubidium and cesium are refined to remove potassium; adding water into the rubidium-cesium mixed precipitate A obtained in the step 4 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: and 2, adding a sodium hydroxide solution to adjust the pH value to 3, stirring and reacting for 1h, adding concentrated hydrochloric acid, adding a tin chloride solution to precipitate when the hydrogen ion concentration is 2mol/L, wherein the mass of the added tin chloride solution is 30% of that of rubidium and cesium in brine, obtaining a rubidium and cesium mixed precipitate B, filtering and separating to obtain brine D, returning the brine D to the step 4 to continue precipitating, and circularly operating the step 3 times, wherein the concentration of rubidium ions and the concentration of potassium ions in the rubidium and cesium mixed precipitate B are 90: 1;
step 6: extracting cesium; adding water into the rubidium-cesium mixed precipitate B obtained in the step 5 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: adding a sodium hydroxide solution until the pH value is 3, performing a stirring reaction, filtering and separating to obtain a mixed solution of tin hydroxide and rubidium and cesium, performing evaporation concentration on the mixed solution of rubidium and cesium until the concentration of cesium ions in the mixed solution of rubidium and cesium is 15g/L, adding concentrated hydrochloric acid, adding an antimony trichloride solution for precipitation when the concentration of hydrogen ions is 2mol/L, adding an antimony trichloride solution with the mass being 130% of the mass of cesium in brine, obtaining cesium chloroantimonate, filtering and separating to obtain a solution E, adding water to the cesium chloroantimonate for size mixing, wherein the mass ratio of the cesium chloroantimonate to the water is 1: 2, adding ammonia water to adjust the pH value to 2, precipitating to obtain antimony hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude cesium chloride, and adding water to recrystallize for 2 times to obtain a cesium chloride product;
and 7: extracting rubidium; adding sodium hydroxide into the solution E to adjust the pH value to 2, precipitating to obtain antimony hydroxide, adding hydrochloric acid into filtrate obtained by filtering and separating, adding a tin tetrachloride solution to precipitate when the concentration of hydrogen ions is 2mol/L, adding 130% of the mass of the tin tetrachloride solution to the mass of rubidium in brine to obtain rubidium stannate chloride precipitate, filtering and separating, adding sodium hydroxide to obtain a solution F and tin hydroxide, returning the solution F to the step 3, adding water into the rubidium stannate precipitate to prepare slurry, wherein the mass ratio of the rubidium stannate precipitate to the water is 1: and 2, adding ammonia water until the pH value is 3, precipitating to obtain tin hydroxide, filtering and separating to obtain filtrate, evaporating to dryness, calcining at 500 ℃ to obtain crude rubidium chloride, and adding water to recrystallize for 2 times to obtain a rubidium chloride product.
And (2) recovering the auxiliary materials obtained in the step, respectively mixing the tin hydroxide precipitated in the step 4, the tin hydroxide separated in the step 6 and the tin hydroxide separated and precipitated in the step 7, adding hydrochloric acid to perform 4-stage countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: 5, returning to the step 3 after filtration and separation for continuous evaporation and concentration;
and (3) adding hydrochloric acid into the antimony hydroxide precipitated in the step (6) to perform countercurrent heat-preservation washing, wherein the washing temperature is 40 ℃, the washing time is 10min, and the mass ratio of the precipitate to the hydrochloric acid is 1: and 5, filtering and separating, returning to the step 3, and continuing to evaporate and concentrate.
The yield of the product extracted by the method for extracting rubidium and cesium from complex underground brine provided by the embodiment is calculated, and table 1 is obtained.
TABLE 1 purity and yield (%)
| /(％) | Main content of cesium chloride | Major content of rubidium chloride | Rubidium comprehensive yield | Overall yield of cesium |
| Example 1 | 99.5 | 99.2 | 80.0 | 75.0 |
| Example 2 | 98.7 | 98.3 | 81.0 | 75.8 |
| Example 3 | 99.2 | 99.0 | 79.6 | 74.5 |
From the above table 1, it can be seen that, in the product extracted by the method for extracting rubidium and cesium from underground brine, the comprehensive yield of rubidium and cesium can reach 80% on average, the comprehensive yield of cesium can reach 75% on average, the main content of rubidium chloride can reach 99.0% on average, and the main content of cesium chloride can reach 99.0% on average; the method for extracting rubidium and cesium by adopting low-concentration enrichment, high-concentration enrichment, evaporation and precipitation avoids the introduction of an organic solvent to generate toxic and harmful substances, effectively reduces the production cost, is simple and convenient to operate, and simultaneously ensures the product yield.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A method for extracting rubidium and cesium from complex underground brine is characterized by sequentially comprising the following steps:
step 1: purifying brine; removing hydrogen sulfide from underground brine, adding lime slurry to precipitate magnesium ions in the underground brine, filtering and separating, and adding a sodium carbonate solution to precipitate calcium ions in the underground brine to obtain brine A;
step 2: rubidium and cesium are primarily enriched; evaporating and concentrating the brine A, separating out sodium chloride, continuing to concentrate until potassium is saturated, adding water, cooling, separating out potassium chloride, acidifying the potassium separation mother liquor to obtain boric acid, extracting bromine and iodine from the boron extraction mother liquor by adopting an air blowing method to obtain brine B, wherein the concentration of rubidium in the brine B is more than 1g/L, and returning to continue evaporating and concentrating;
and step 3: rubidium and cesium are deeply enriched; when the concentration of lithium ions in the brine B is more than 15g/L, adding a sodium carbonate solution to precipitate the lithium ions after the calcium ions and the magnesium ions are removed; and if the concentration of the lithium ions is less than 15g/L, independently performing evaporation concentration to separate out sodium chloride, cooling to separate out potassium chloride, filtering and separating until the concentration of the lithium ions in the mother liquor is more than 15g/L, precipitating lithium, and returning the mixture of the separated sodium chloride and potassium chloride to the step 2 for evaporation concentration after the mixture is dissolved back in water. Precipitating lithium to obtain brine C, wherein the concentration of rubidium in the brine C is 10-20 g/L, and if the rubidium concentration in the brine C cannot be reached, returning to continue evaporating and concentrating;
and 4, step 4: precipitating rubidium and cesium; adding concentrated hydrochloric acid into the brine C until the hydrogen ion concentration is 0-5 mol/L, adding a stannic chloride solution for precipitation to obtain a rubidium-cesium mixed precipitate A, adding a saturated sodium hydroxide solution into the brine C from which rubidium and cesium are removed, precipitating to obtain stannic hydroxide, and returning the filtered and separated mother liquor to the step 3 for continuous evaporation and concentration;
and 5: rubidium and cesium are refined to remove potassium; adding water into the rubidium-cesium mixed precipitate A obtained in the step 4 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: (1-10), adding a sodium hydroxide solution to adjust the pH value, stirring and reacting, adding concentrated hydrochloric acid, adding a tin chloride solution to precipitate when the hydrogen ion concentration is 0-5 mol/L, and obtaining a rubidium-cesium mixed precipitate B, wherein the concentration of rubidium ions and the concentration of potassium ions in the rubidium-cesium mixed precipitate B are 10-100: 1, if not, returning to the step 5 until the concentration of the precipitate reaches the standard, filtering and separating to obtain a solution D, adding a saturated sodium hydroxide solution into the solution D, precipitating to obtain tin hydroxide, and returning the filtered and separated mother liquor to the step 3 to continue evaporation and concentration;
step 6: extracting cesium; adding water into the rubidium-cesium mixed precipitate B obtained in the step 5 for size mixing, wherein the mass ratio of the rubidium-cesium mixed precipitate A to the water is 1: (1-10), adding a sodium hydroxide solution until the pH value is 0-7, performing stirring reaction, filtering and separating to obtain a mixed solution of tin hydroxide and rubidium and cesium, performing evaporation concentration on the mixed solution of rubidium and cesium, adding concentrated hydrochloric acid when the concentration of cesium ions in the mixed solution of rubidium and cesium is 10-20 g/L, adding an antimony trichloride solution when the concentration of hydrogen ions is 0-5 mol/L, performing precipitation to obtain cesium chloroantimonate, filtering and separating to obtain a solution E, adding water to the cesium chloroantimonate, and pulping, wherein the mass ratio of the cesium chloroantimonate to the water is 1: (1-10), adding ammonia water to adjust the pH value, precipitating to obtain antimony hydroxide, filtering and separating to obtain filtrate, evaporating to dryness and calcining to obtain crude cesium chloride, and adding water to recrystallize to obtain a cesium chloride product;
and 7: extracting rubidium; adding sodium hydroxide into the solution E for precipitation to obtain antimony hydroxide, adding hydrochloric acid into filtrate obtained by filtering and separating, adding a tin tetrachloride solution for precipitation when the concentration of hydrogen ions is 0-5 mol/L, obtaining rubidium chlorostannate precipitate, continuously adding sodium hydroxide into mother liquor obtained by filtering and separating to obtain solution F and tin hydroxide, returning the solution F to the step 3, adding water into the rubidium chlorostannate precipitate for size mixing, wherein the mass ratio of the rubidium chlorostannate precipitate to the water is 1: (1-10), adding ammonia water until the pH value is 0-7, precipitating to obtain tin hydroxide, filtering and separating to obtain filtrate, evaporating to dryness and calcining to obtain crude rubidium chloride, and adding water to recrystallize to obtain a rubidium chloride product.
2. The method of claim 1, wherein the auxiliary materials obtained from the method for extracting rubidium and cesium from the underground brine are recovered, and the tin hydroxide precipitated in step 4, the tin hydroxide separated in step 6, and the tin hydroxide separated and precipitated in step 7 are mixed, washed, purified, and dissolved in hydrochloric acid for further use.
Washing the antimony hydroxide precipitated in the step 6, and adding hydrochloric acid to dissolve back for later use.
3. The method for extracting rubidium and cesium from complex underground brine according to claim 1, wherein said cooling in step 3 is performed to separate potassium chloride, and the temperature of cooling is in the range of 20-60 ℃.
4. The method of claim 1, wherein step 5 comprises adding sodium hydroxide solution to adjust pH, which ranges from 0 to 7.
5. The method of claim 1, wherein ammonia is added in steps 6 and 7 to adjust pH, which ranges from 0 to 7.
6. The method for extracting rubidium and cesium from complex underground brine according to claim 1, wherein the molar mass of the solution of stannic chloride added in step 4 is 120% -180% of the molar mass of rubidium and cesium ions.
7. The method for extracting rubidium and cesium from complex underground brine according to claim 1, wherein the molar mass of the added stannic chloride solution in step 5 is 10% -30% of the molar mass of rubidium and cesium ions.
8. The method for extracting rubidium and cesium from complex underground brine according to claim 1, wherein said step 6 of adding antimony trichloride solution with molar mass 110% -130% of that of cesium ions.
9. The method for extracting rubidium and cesium from complex underground brine according to claim 1, wherein the molar mass of the solution of stannic chloride added in step 7 is 110% -130% of the molar mass of rubidium ions.
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| CN112239221A (en) * | 2020-10-19 | 2021-01-19 | 广东省科学院资源综合利用研究所 | Method for extracting rubidium chloride from rubidium-containing high-salinity brine |
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