CN113307299A - Method for extracting rubidium from high-potassium magnesium chloride brine - Google Patents
Method for extracting rubidium from high-potassium magnesium chloride brine Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
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- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
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- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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Abstract
The invention discloses a method for extracting rubidium from high-potassium magnesium chloride brine. The method comprises the following steps: crystallizing high-potassium magnesium chloride brine by blending and evaporating technologies to form carnallite, removing impurity minerals to obtain high-grade low-sodium carnallite, and then producing potassium chloride by using a carnallite cold decomposition method; adding water into potassium chloride for dissolving, performing solid-liquid separation again to obtain a primary rubidium-rich liquid and potassium chloride, performing evaporation concentration on the primary rubidium-rich liquid, crystallizing to separate out potassium chloride, performing solid-liquid separation to obtain a secondary rubidium-rich liquid, adjusting the pH value of the secondary rubidium-rich liquid by using an alkaline substance, precipitating partial magnesium carbonate or magnesium hydroxide to obtain a basic tertiary rubidium-rich liquid, performing extraction and back extraction treatment by using rubidium ions in the organic relative basic tertiary rubidium-rich liquid to obtain a back-extraction four-stage rubidium-rich liquid, and performing evaporation treatment to crystallize and separate out rubidium salt. The invention can separate rubidium ions from most potassium ions by accurately controlling the partial dissolution-crystallization process of the rubidium-containing salt lake potassium chloride.
Description
Technical Field
The invention relates to a method for extracting rubidium from brine resources, in particular to a method for extracting rubidium from high-potassium magnesium chloride brine at low cost, and belongs to the technical field of salt lake chemistry and chemical engineering.
Background
Rubidium is an element with excellent chemical property and photoelectric property, is an important rare metal and an emerging industrial mineral product with strategy, and has important application in new energy and high and new technology fields such as atomic clocks, catalysts, magnetofluids, thermionic power generation, photovoltaic cells and the like. Rubidium salts such as rubidium chloride, rubidium nitrate, rubidium sulfate and rubidium carbonate as basic raw materials of rubidium industry have high value. Abundant rubidium resources are stored in salt lakes and underground brine in China. Wherein, the concentration of rubidium in the saline water of the Chelidwood basin Kerr sweat lake and the saline water of the oilfield under the south wing mountain land of Qinghai province is higher than 10mg/L and is more than 100 times higher than that of the seawater, and the rubidium-enriched source is a good rubidium-enriched resource. Meanwhile, the reserves of rubidium in the brine are huge and exceed dozens of thousands of tons. For example, the rubidium chloride loss in the production process of potassium chloride in the Carlo salt lake is more than 300 tons each year and has a value of over 15 hundred million. If the rubidium salt can be extracted economically and efficiently to prepare a corresponding rubidium salt product, the rubidium salt product has a considerable economic value. However, besides trace rubidium, the brine also contains a large amount of components such as Na, K, Mg, Ca and the like in an amount of tens to hundreds of g/L, and the extraction of rubidium is difficult and the cost is high.
Currently, known rubidium salt extraction methods mainly include an ion exchange/adsorption method, an extraction method, a precipitation method and the like, and mainly aim at raw materials such as radioactive wastewater, pollucite leachate, lepidolite lithium precipitation mother liquor and low-magnesium-calcium type brine. However, when the method is used for extracting rubidium from high-potassium magnesium (and/or calcium) brine, the limitation is large, the comprehensive utilization and combination degree with salt lake resources is poor, the method is directly used for the actual production process of a system with trace rubidium and a large amount of impurities such as potassium, magnesium, calcium and the like, the production cost is extremely high, and the economic requirement of products cannot be met. For example, chinese patent CN 1094332a discloses an enrichment extraction method of rubidium in brine, which uses copper nitrate and potassium ferricyanide to synthesize an ion exchanger, and is used for enriching and extracting rubidium before salt making of brine used in salt making enterprises, and the primary adsorption rate is high, but the concentration of rubidium in eluent obtained by the method is low, and the potassium content is still very high (the weight ratio of potassium to rubidium is-40: 1), and the subsequent evaporation and purification processes are complex, and the production cost is still high. In addition, the weight ratio of potassium to rubidium in the rubidium extracting liquid applicable to the method is only 135:1, the rubidium extracting liquid belongs to brine with low potassium to rubidium ratio, and the applicability of the rubidium extracting liquid to brine with high potassium to rubidium ratio (>1000:1) is still to be investigated.
Chinese patent CN 109824068A discloses a method for extracting Rb from low-concentration brine and preparing a high-purity rubidium salt, in which ammonium phosphomolybdate and ammonium phosphotungstate are prepared into rubidium ion adsorption microspheres together with polyvinyl alcohol, sodium alginate and sodium silicate, and the rubidium ion adsorption microspheres are filled into an adsorption column for adsorbing rubidium ions from rubidium-containing brine, and an ammonium salt solution is used for desorption to obtain a rubidium-enriched feed liquid. However, this patent does not disclose the concentration of potassium ions in the raw material solution, and only indicates that the rubidium ion concentration needs to be 40mg/L or more. In the literature, "research on process for extracting rubidium ions from ammonium phosphomolybdate" (caohuadonmei, salt industry and chemical industry, 2014, 43, 22-24.), it is clearly indicated that the effect of coexisting potassium ions on adsorbing rubidium ions by the ammonium phosphomolybdate adsorbent has a significant negative effect, when the potassium concentration is 0.8g/L and the rubidium concentration is 1.7g/L, the exchange amount of ammonium phosphomolybdate for rubidium ions can be reduced by more than 10%, and the effect of high-concentration potassium ions on the adsorption effect of low-concentration rubidium ions in high-potassium-rubidium-ratio brine (>1000:1) is inevitably greater, even the adsorbent almost loses the adsorption effect on rubidium ions.
Chinese patent CN 86101311 a discloses a process for extracting rubidium and cesium from weathered shells of acidic and alkaline rock magma or ion-exchange rare earth ores, which uses a bispiclamide-nitrobenzene extraction method to recover rubidium and cesium, but the used extractant has high toxicity and poor selectivity, which limits the application and development of the extractant to a great extent. The method has good extraction and separation effects only in weak alkalinity (pH 8-9), and the high-magnesium-calcium brine is usually weakly acidic. Furthermore, the method does not examine the effect of potassium on rubidium and cesium extraction and separation.
Chinese patent CN 101987733A discloses a lithium ionA method for separating potassium and rubidium from mica treatment liquid is disclosed, wherein high-concentration magnesium chloride is added into lepidolite treatment liquid, potassium and rubidium are separated from the solution together in the form of carnallite, the obtained potassium and rubidium carnallite crystals are heated and dissolved in water, the pH value is adjusted to 11-13 by NaOH, and most of Mg is Mg (OH)2Separating the precipitate to obtain a mother solution which is a mixed solution of potassium chloride and rubidium chloride. The method comprises the following steps: (ii) almost all of the Mg needs to be replaced with Mg (OH)2The precipitate is separated out, and a large amount of NaOH is consumed in the process; ② all potassium and rubidium enter carnallite together, and are used as raw materials for potassium-rubidium extraction and separation after magnesium removal, and potassium and rubidium are not separated completely in the process.
Chinese patent CN 103787375A discloses a method for extracting rubidium salt and cesium salt from a high-salinity solution by using a t-BAMBP substituted phenol extraction agent, but the method needs to adjust the pH value of the system to 11-14, and when the method is applied to high-magnesium-calcium brine, the pretreatment process of brine pH adjustment has huge alkali consumption due to magnesium and calcium precipitation and extremely high rubidium recovery cost although the separation effect of rubidium and potassium is good. The extraction technologies reported in patents CN 104789800A and CN 105256150A still have the problem of high rubidium extraction cost when used in high magnesium system because the extraction system is still t-BAMBP substituted phenol extractant, although the reagent consumption of the method for precipitating magnesium by using active carbonate is slightly lower than that of sodium hydroxide, the cost improvement is not significant; the latter method adopts calcium and magnesium ion chelating resin to remove calcium and magnesium in brine, which is feasible and economical for low-calcium and magnesium brine, but has high cost for removing calcium and magnesium from high-magnesium and calcium brine (such as Qinghai Kerr salt lake and deep-layer brine of southern wing mountain, etc.), and has difficulty in economically recovering rubidium from high-magnesium and calcium brine. Patent CN 107460344 a discloses a new method for extracting rubidium from brine by using t-BAMBP extractant, which can reduce the amount of alkali needed for directly adjusting the pH of brine to a certain extent by saponification treatment. However, the pH of the raffinate obtained in the method is still about 12, and the alkalinity lost by hydrolysis of the saponification extracting agent is still considerable. In addition, the technology is still only suitable for brine with low magnesium and calcium, and in a related document of the technology [ Zhang Jian, efficient separation and extraction of rubidium and cesium resources in salt lake brine, 2018], the inventor removes high magnesium and calcium in brine by adding calcium oxide and oxalic acid and then extracts the high magnesium and calcium, and the extraction pretreatment cost of the step is still extremely high because the contents of magnesium and calcium are higher by several orders of magnitude than those of rubidium and cesium. Patent CN 105664845 a discloses a rubidium ion-compatible adsorbent of activated zeolite and ammonium phosphomolybdate, but it still continues the respective disadvantages of these two adsorbents, i.e. it needs to use high-concentration ammonium salt solution (such as ammonium nitrate, ammonium chloride, etc.) for desorption, and the concentration of rubidium in desorption solution is polar and the concentration of ammonium is extremely high, and it is still a high energy consumption link for both subsequent concentration crystallization and rubidium/ammonium separation. Patent CN 106145242 a discloses a novel cyclic ether extractant capable of simultaneously separating potassium, rubidium, cesium and strontium ions from salt lake brine, but the separation capability of the method is poor, and even if these elements are simultaneously separated out of the brine system, the subsequent separation for obtaining respective corresponding products is still a problem. U.S. Pat. No. 4, 7,323,150, 2 discloses a method for enriching Li, Rb, Cs plasma in pollucite by repeated roasting, leaching and carbon dioxide bubbling precipitation, but the method is not suitable for salt lake brine systems with high magnesium and calcium content and low rubidium content.
In addition, ion exchange/adsorption and solvent extraction are the methods of extracting rubidium from brine which are considered to have the greatest application prospects. However, the ion exchange/adsorption method usually requires desorption using a high-concentration ammonium salt solution, and the concentration capacity of the desorption solution is large and the energy consumption of ammonium burning is high due to the low rubidium concentration in the desorption solution. Taking the desorption solution with 100mg/L rubidium concentration and 72g/L ammonium concentration as an example, the energy consumption cost of only evaporating and burning ammonium for every 1kg of recovered rubidium chloride is nearly ten thousand yuan, which exceeds the value of the rubidium chloride. Solvent extraction algorithms tend to be difficult to adapt to the low rubidium concentration, near neutral pH, and extremely high potassium, magnesium, and calcium components of brines. 4-tert-butyl-2-alpha-methylbenzylphenol (t-BAMBP) is one of rubidium extracting agents which are most researched and widely applied at present, has better rubidium and potassium separation capacity, but needs to adjust the pH value of a system to 13-14 in use, and is mostly applied to an alkaline carbonate system after lithium is extracted from lepidolite. For example, from the brine of the salt lake of Chaer, its raw brine andthe mother liquor for decomposing carnallite is a nearly neutral system, and the rubidium concentration is extremely low (<50Mg/L) and Mg concentration is extremely high, 7000 and 1000 times the Rb concentration, respectively. During the pretreatment for pH adjustment prior to extraction, Mg forms Mg (OH)2Or MgCO3Precipitation, consumption of large amount of NaOH or Na2CO3Therefore, the comprehensive cost is high; on the other hand, Mg (OH) formed2Or MgCO3The entrainment of the precipitation mother liquor is extremely large (40-80 percent), partial rubidium ions in the solution can be carried away, the loss is caused, and the rubidium yield is reduced.
Obviously, the existing mode for extracting rubidium salt can only be applied to a low-magnesium aqueous solution system, and the economic benefit cannot be obtained due to the fact that the comprehensive extraction cost is too high due to the high magnesium treatment cost for extracting trace rubidium from brine of a high-potassium and magnesium system.
Disclosure of Invention
The invention mainly aims to provide a method for extracting rubidium from high-potassium magnesium chloride brine, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for extracting rubidium from high-potassium magnesium chloride brine, which comprises the following steps:
(1) crystallizing high-potassium magnesium chloride brine to form carnallite ore by brine blending and evaporation technologies, removing sodium chloride impurity minerals by using a flotation technology to obtain high-grade low-sodium carnallite, and then producing potassium chloride by using a carnallite cold decomposition method, wherein the grade of the potassium chloride is more than 90%, the sodium content is lower than 5 wt%, the magnesium content is lower than 5 wt%, and the water content is lower than 10 wt%;
(2) adding water into the potassium chloride obtained in the step (1) for partial dissolution at the temperature of 0-100 ℃, then carrying out solid-liquid separation to obtain a first-stage rubidium-rich liquid and potassium chloride, and drying the potassium chloride to obtain a fertilizer-grade product; wherein the concentration of rubidium ions in the first-stage rubidium-rich liquid is 30-100 mg/L, the concentration of potassium ions is 60-200 g/L, the concentration of sodium ions is 0.5-8 g/L, and the concentration of magnesium ions is 0.5-5 g/L;
(3) evaporating and concentrating the primary rubidium-rich liquid obtained in the step (2), crystallizing and precipitating potassium chloride with the purity of more than 99%, and performing solid-liquid separation to obtain a secondary rubidium-rich liquid, wherein the concentration of rubidium ions in the secondary rubidium-rich liquid is 500-2000 mg/L, the concentration of potassium ions is 80-200 g/L, the concentration of magnesium ions is 10-120 g/L, and the concentration of sodium ions is 20-100 g/L;
(4) adjusting the pH value of the secondary rubidium-rich liquid obtained in the step (3) to 8-14 by using an alkaline substance, and precipitating partial magnesium carbonate or magnesium hydroxide to obtain a primary tertiary rubidium-rich liquid, wherein the concentration of rubidium ions in the primary tertiary rubidium-rich liquid is 400-1800 mg/L, the concentration of potassium ions is 70-190 g/L, the concentration of magnesium ions is 0.5-10 g/L, and the concentration of sodium ions is 15-60 g/L, wherein the alkaline substance comprises a solid or solution of hydroxide or carbonate of alkali metal or alkaline earth metal, the alkaline substance comprises any one or a combination of more than two of calcium hydroxide, calcium oxide, sodium bicarbonate and sodium carbonate, and the reaction temperature for precipitating magnesium is 10-100 ℃;
(5) carrying out extraction and back extraction treatment on rubidium ions in the alkaline tertiary rubidium-rich liquid obtained in the step (4) by adopting an organic phase consisting of a t-BAMBP extractant and a diluent to obtain a back-extraction quaternary rubidium-rich liquid, wherein the concentration of the rubidium ions in the back-extraction quaternary rubidium-rich liquid is 2000-90000 mg/L, the concentration of potassium ions is lower than 5000mg/L, the concentration of sodium ions is lower than 1000mg/L, and the total concentration of magnesium and calcium ions is lower than 1000 mg/L;
(6) and (3) evaporating the back-extracted four-stage rubidium-enriched liquid obtained in the step (5) to crystallize and precipitate rubidium salt, so that rubidium is extracted, wherein the purity of the obtained product rubidium chloride is more than 90%, the potassium content is lower than 3 wt%, the sodium content is lower than 2 wt%, and the magnesium and calcium contents are lower than 1 wt%.
In some preferred embodiments, the concentration of potassium ions in the high-potassium magnesium chloride brine is above 5g/L, the concentration of magnesium ions is above 10g/L, and the concentration of rubidium ions is above 5 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through accurate control of the partial dissolution-crystallization process of rubidium-containing salt lake potassium chloride, rubidium ions are separated from most of potassium ions, magnesium ions and sodium ions, meanwhile, the concentration of rubidium in a liquid phase is increased from 10mg/L in salt lake brine to more than hundreds of mg/L, the material amount required to be treated in subsequent extraction is reduced by hundreds of times, the magnesium removal cost is greatly reduced, and thus the comprehensive cost for extracting rubidium is reduced; finally, the process of partially dissolving and crystallizing the potassium chloride in the rubidium-containing salt lake is equivalent to one-time refining of potassium chloride products, the purity of the potassium chloride products can be improved while the yield of the potassium chloride is hardly lost, and the influence on the production process of the potassium chloride is extremely small.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of an embodiment of the present invention provides a method for extracting rubidium from high-potassium magnesium chloride brine, comprising:
(1) crystallizing high-potassium magnesium chloride brine to form carnallite ore by brine blending and evaporation technologies, removing sodium chloride impurity minerals by using a flotation technology to obtain high-grade low-sodium carnallite, and then producing potassium chloride by using a carnallite cold decomposition method, wherein the grade of the potassium chloride is more than 90%, the sodium content is lower than 5 wt%, the magnesium content is lower than 5 wt%, and the water content is lower than 10 wt%;
(2) adding water into the potassium chloride obtained in the step (1) for partial dissolution at the temperature of 0-100 ℃, then carrying out solid-liquid separation to obtain a first-stage rubidium-rich liquid and potassium chloride, and drying the potassium chloride to obtain a fertilizer-grade product; wherein the concentration of rubidium ions in the first-stage rubidium-rich liquid is 30-100 mg/L, the concentration of potassium ions is 60-200 g/L, the concentration of sodium ions is 0.5-8 g/L, and the concentration of magnesium ions is 0.5-5 g/L;
(3) evaporating and concentrating the primary rubidium-rich liquid obtained in the step (2), crystallizing and precipitating potassium chloride with the purity of more than 99%, and performing solid-liquid separation to obtain a secondary rubidium-rich liquid, wherein the concentration of rubidium ions in the secondary rubidium-rich liquid is 500-2000 mg/L, the concentration of potassium ions is 80-200 g/L, the concentration of magnesium ions is 10-120 g/L, and the concentration of sodium ions is 20-100 g/L;
(4) adjusting the pH value of the secondary rubidium-rich liquid obtained in the step (3) to 8-14 by using an alkaline substance, and precipitating partial magnesium carbonate or magnesium hydroxide to obtain a primary tertiary rubidium-rich liquid, wherein the concentration of rubidium ions in the primary tertiary rubidium-rich liquid is 400-1800 mg/L, the concentration of potassium ions is 70-190 g/L, the concentration of magnesium ions is 0.5-10 g/L, and the concentration of sodium ions is 15-60 g/L, wherein the alkaline substance comprises a solid or solution of hydroxide or carbonate of alkali metal or alkaline earth metal, the alkaline substance comprises any one or a combination of more than two of calcium hydroxide, calcium oxide, sodium bicarbonate and sodium carbonate, and the reaction temperature for precipitating magnesium is 10-100 ℃;
(5) carrying out extraction and back extraction treatment on rubidium ions in the alkaline tertiary rubidium-rich liquid obtained in the step (4) by adopting an organic phase consisting of a t-BAMBP extractant and a diluent to obtain a back-extraction quaternary rubidium-rich liquid, wherein the concentration of the rubidium ions in the back-extraction quaternary rubidium-rich liquid is 2000-90000 mg/L, the concentration of potassium ions is lower than 5000mg/L, the concentration of sodium ions is lower than 1000mg/L, and the total concentration of magnesium and calcium ions is lower than 1000 mg/L;
(6) and (3) evaporating the back-extracted four-stage rubidium-enriched liquid obtained in the step (5) to crystallize and precipitate rubidium salt, so that rubidium is extracted, wherein the purity of the obtained product rubidium chloride is more than 90%, the potassium content is lower than 3 wt%, the sodium content is lower than 2 wt%, and the magnesium and calcium contents are lower than 1 wt%.
In some embodiments, the method of extracting rubidium from high potassium magnesium chloride brine comprises the steps of:
(1) crystallizing high-potassium magnesium chloride brine to form carnallite ore by controlling the processes of brine blending and evaporation, removing impurity minerals in the carnallite ore by ore dressing to obtain high-grade carnallite, and producing potassium chloride by using a carnallite cold decomposition method; (2) adding a proper amount of water into the potassium chloride obtained in the step (1) for partial dissolution, and filtering to obtain a first-stage rubidium-rich liquid and a high-purity potassium chloride product; (3) evaporating and concentrating the first-stage rubidium-rich liquid obtained in the step (2) for several times at a certain temperature, crystallizing and separating out high-purity potassium chloride, and simultaneously obtaining a second-stage rubidium-rich liquid, wherein the concentration of rubidium is 500 mg/L-2000 mg/L; (4) adding alkaline substances (such as sodium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate, potassium carbonate and the like) into the secondary rubidium-enriched liquid obtained in the step (3) at a certain temperature, and adjusting the pH value to 11-14 to obtain an alkaline tertiary rubidium-enriched liquid; (5) extracting and back-extracting rubidium from an organic relatively alkaline tertiary rubidium-rich liquid consisting of t-BAMBP extractant and kerosene to obtain a back-extraction quaternary rubidium-rich liquid with the rubidium concentration of 2000 mg/L-90000 mg/L; (6) and (3) carrying out evaporative crystallization (natural evaporation or forced evaporation) on the four-stage rubidium-enriched liquid obtained in the step (5), crystallizing and precipitating rubidium salt, and drying to obtain a rubidium salt product.
In some embodiments, in step (1), the potassium ion concentration in the high potassium magnesium chloride brine is above 5g/L (K)+The concentration is more than or equal to 5g/L), the concentration of magnesium ions is more than 10g/L (Mg)2+The concentration is more than or equal to 10g/L), the concentration of rubidium ions is more than 5mg/L (Rb)+The concentration is more than or equal to 5 mg/L).
In some embodiments, in the step (2), the mass ratio of the added water to the potassium chloride is 0.5: 1-1.5: 1, and the dissolving temperature is 0-60 ℃.
Further, in the step (2) and the step (3), the solid-liquid separation method is filtration, sedimentation overflow, centrifugal separation, or the like, but is not limited thereto.
In some embodiments, in the step (3), the temperature of the evaporation concentration is 0 ℃ to 110 ℃, and the concentration multiple is 5-50 times.
In some embodiments, in step (4), the molar ratio of the alkaline substance to the magnesium ions in the secondary rubidium-rich liquid is 1-3: 1, the reaction temperature for precipitating magnesium is 20-80 ℃.
Further, in the step (4), the alkaline substance is a solid or a solution of an alkali metal carbonate or hydroxide, such as sodium hydroxide, potassium hydroxide, calcium oxide, sodium bicarbonate, sodium carbonate, potassium carbonate, and the like, and the ratio of the addition amount of the alkaline substance to the amount of the magnesium substance in the solution is 1-3: 1, the reaction temperature is 10-100 ℃.
In some embodiments, in the step (5), the organic phase for extraction is formed by mechanically stirring and uniformly mixing 5-45% by volume of t-BAMBP extractant and 55-95% by volume of diluent at room temperature.
Further, the t-BAMBP-based extractant includes any one or a combination of two or more of 4-methyl-2 (α -methylbenzyl) phenol, 4-ethyl-2 (α -methylbenzyl) phenol, 4-isopropyl-2 (α -methylbenzyl) phenol, 4-sec-butyl-2 (α -methylbenzyl) phenol, and 4-tert-butyl-2 (α -methylbenzyl) phenol, and the like, but is not limited thereto.
Further, the diluent includes any one or a combination of two or more of 120 # solvent oil, 160 # solvent oil, 200 # solvent oil, D70 special solvent oil, D80 special solvent oil, aviation kerosene, sulfonated kerosene and the like, but is not limited thereto.
Further, the extraction conditions were: the volume ratio of the alkaline tertiary rubidium-rich liquid to the organic phase for extraction is 1: 4-4: 1, and the extraction temperature is 10-40 ℃.
In some embodiments, in step (5), the stripping process comprises: and (4) carrying out back extraction treatment on the extracted system by using a mixture of an organic phase and a back extractant.
The stripping agent is an aqueous acid solution containing a predetermined rubidium salt product anion at a molar concentration of 0.1 to 6.0mol/L, and preferably includes, for example, one or a combination of two or more of formic acid, acetic acid, nitric acid, hydrochloric acid, hydrobromic acid, carbonic acid, and sulfuric acid, but is not limited thereto.
Further, the temperature of the extraction operation is 10 ℃ to 40 ℃.
Further, the volume ratio of the organic phase to the stripping agent is 1: 1-50: 1.
In some embodiments, in step (6), the temperature of the evaporation treatment is from 20 ℃ to 100 ℃.
In some embodiments, step (6) specifically comprises: naturally evaporating the back-extracted four-stage rubidium-enriched liquid obtained in the step (5) or forcibly evaporating the back-extracted four-stage rubidium-enriched liquid by a multi-effect evaporator so as to crystallize and precipitate rubidium salt, and drying the obtained rubidium salt crystal to obtain a rubidium salt product; wherein the drying temperature is 80-160 ℃.
Further, the evaporation temperature of the back-extraction four-stage rubidium-rich liquid in the step (6) is 20-100 ℃, the evaporation condition can be room-temperature natural evaporation or forced evaporation of a multi-effect evaporator, the obtained rubidium salt crystal is dried at 10-100 ℃, and the purity of the obtained rubidium salt product is not lower than 90%.
In conclusion, the rubidium salt lake potassium chloride partial dissolution-crystallization process is accurately controlled, so that rubidium ions are separated from most potassium ions, meanwhile, the concentration of rubidium in a liquid phase is increased from 10mg/L in salt lake brine to hundreds of mg/L, the amount of materials required to be treated in subsequent extraction is reduced by hundreds of times, the magnesium removal cost is greatly reduced, and the comprehensive cost for extracting rubidium is reduced; finally, the partial dissolution-crystallization process of the rubidium-containing salt lake potassium chloride is equivalent to one-time refining of the potassium chloride product, the purity of the potassium chloride product can be improved while the yield of the potassium chloride is hardly lost, and the influence on the production process of the potassium chloride is extremely small (the content ranges are shown in table 1).
TABLE 1
The present invention is further illustrated by the following specific examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
Providing 40L of brine containing rubidium, high potassium and magnesium chloride, wherein Rb is+The concentration is 9.1mg/L, Na+The concentration is 16.0g/L, K+The concentration is 15.1g/L, Mg2+Concentration of 46g/L, Ca2+The concentration was 0.2 g/L. Evaporating 40L bittern to residual 28.3kg, adding old bittern 10kg (Na component)+The concentration is 2.3g/L, K+Concentration of 0.5g/L, Mg2+Concentration of 106g/L, Ca2+Concentration of 0.57g/L) was evaporated further, the brine was crystallized to form 5.73kg of carnallite of grade 77%. Removing NaCl impurities in the carnallite ore by flotation to obtain the grade of 99 percentAdding 2.07L of water into the carnallite to decompose and produce potassium chloride, and simultaneously circularly decomposing a mother solution to obtain 1.01kg of potassium chloride; rb in the obtained potassium chloride+0.025 wt%, 0.53 wt% sodium, 97 wt% KCl, and Mg2+The content is 0.1 wt%;
adding 400g of water into 500g of potassium chloride obtained above, partially dissolving at 25 ℃, filtering to obtain 337g of high-purity potassium chloride product as a solid phase and 611g of first-stage rubidium-rich liquid as a liquid phase, wherein Rb is+The concentration is 98mg/L, K+The concentration is 165.5g/L, Mg2+The concentration is 0.98g/L, Na+The concentration is 5.2 g/L;
the obtained first order rubidium-rich liquid 611g is evaporated and concentrated at 90 ℃, the temperature is reduced to room temperature (about 20 ℃), precipitated potassium chloride (purity is 99.3 wt%) is filtered out, and the remaining second order rubidium-rich liquid 25g is obtained, wherein Rb is+The concentration is 880mg/L, K+The concentration is 125g/L, Mg2+The concentration is 21.5g/L, Na+The concentration was 46 g/L. Adding 6.4g of 30 wt% sodium hydroxide solution into the secondary rubidium-rich solution at room temperature according to 1.1 times of the amount of magnesium ion substances, wherein the pH value of a liquid phase reaches 13.7, the reaction temperature of precipitated magnesium is 40 ℃, performing solid-liquid separation on the obtained mixed reactant, the separated solid phase is 1.5g of magnesium hydroxide, and the separated liquid phase is 27g of alkaline tertiary rubidium-rich solution, wherein Rb is+The concentration is 772mg/L, K+The concentration is 101g/L, Mg2+The concentration is 0.6g/L, Na+The concentration is 39 g/L;
adding 30% t-BAMBP-sulfonated kerosene organic phase into the alkaline tertiary rubidium-enriched liquid according to the volume ratio of O/A of 2:1, and performing extraction treatment at 20 ℃ to form a loaded organic phase; then carrying out back extraction treatment at 20 ℃ by using 1mol/L HCl according to the ratio of 20:1 to obtain back extraction four-stage rubidium-rich liquid, wherein Rb is+The concentration is 7.7g/L, K+The concentration is 0.25g/L, Na+Has a concentration of 0.9g/L, Mg2+、Ca2+The total concentration of (A) is 0.5 g/L;
and (3) evaporating the obtained four-stage rubidium-enriched liquid at 70 ℃, and drying the obtained rubidium salt crystal at 80 ℃ to obtain a rubidium salt product, wherein the product purity is 95.02%.
Example 2
The present embodiment is different from embodiment 1 in that:
250g of potassium chloride obtained in example 1, in which Rb is used+0.025 wt%, 0.53 wt% sodium, 97 wt% KCl, and Mg2+0.1 wt% of calcium, 0.14 wt% of calcium, 125g of water, and the mixture is partially dissolved at 0 ℃, the solid phase after filtration is 225g of high-purity potassium chloride product, and the liquid phase is 125g of first-stage rubidium-rich liquid, wherein Rb is+The concentration is 70mg/L, K+The concentration is 107g/L, Mg2+The concentration is 0.94g/L, Na+The concentration was 4.9 g/L.
Example 3
The present embodiment is different from embodiment 1 in that:
250g of potassium chloride obtained in example 1, in which Rb is used+0.025 wt%, 0.53 wt% sodium, 97 wt% KCl, and Mg2+0.1 wt% of calcium, 0.14 wt% of calcium, 375g of water, and 195g of high-purity potassium chloride product after filtration, 155g of first-stage rubidium-rich liquid as liquid phase, wherein Rb is+The concentration is 88mg/L, K+Concentration 198g/L, Mg2+The concentration is 0.95g/L, Na+The concentration was 5.1 g/L.
Example 4
The present embodiment is different from embodiment 2 in that:
125g of the first rubidium-rich liquid obtained in example 2 was taken, wherein Rb is+The concentration is 70mg/L, K+The concentration is 107g/L, Mg2 +The concentration is 0.94g/L, Na+Evaporating at 0 deg.C to 21.5g with concentration of 4.9g/L, and performing solid-liquid separation to obtain 11g of potassium chloride with purity of 99.6%, and secondary rubidium-rich liquid 10g, wherein Rb is+The concentration is 630mg/L, K+The concentration is 103g/L, Mg2+The concentration is 11.75g/L, Na+The concentration was 61 g/L.
Example 5
The present embodiment is different from embodiment 3 in that:
155g of the first rubidium-rich liquid obtained in example 3 was taken, wherein Rb is+The concentration is 88mg/L, K+Concentration 198g/L, Mg2 +The concentration is 0.95g/L, Na+The concentration is 5.1g/L, the mixture is evaporated to 17g at 110 ℃, and solid-liquid separation is carried out to obtain 10g of potassium chloride with the purity of 99.6 percent and 7g of secondary rubidium-rich liquid, wherein Rb is+The concentration is 1900mg/L, K+At a concentration of 187g/L, Mg2+The concentration is 19g/L, Na+The concentration was 58 g/L.
Example 6
This embodiment is different from embodiment 5 in that:
7g of the secondary rubidium-rich liquid obtained in example 5 was taken, wherein Rb is+The concentration is 1900mg/L, K+At a concentration of 187g/L, Mg2 +The concentration is 19g/L, Na+The concentration is 58g/L, 0.35g of calcium oxide is added into the mixture, the mixture reacts at the temperature of 25 ℃ to form magnesium carbonate precipitate, and the precipitate is filtered to obtain 6.5g of alkaline tertiary rubidium-enriched liquid, wherein Rb is Rb+The concentration is 1800mg/L, K+The concentration is 180g/L, Mg2+The concentration is 0.6g/L, Na+The concentration was 54 g/L.
Example 7
This embodiment is different from embodiment 6 in that:
the molar ratio of calcium oxide to magnesium ions in the secondary rubidium-enriched liquid is 1:1, and the reaction temperature of precipitated magnesium is 10 ℃;
adding 5% t-BAMBP-sulfonated kerosene organic phase into the obtained alkaline tertiary rubidium-rich liquid according to the volume ratio of O/A of 1:4, and performing extraction treatment at 40 ℃ to form a loaded organic phase; then carrying out back extraction treatment at 20 ℃ by using 0.1mol/L HCl according to the ratio of 1:1 to obtain back extraction four-stage rubidium-rich liquid, wherein Rb is+The concentration is 85g/L, K+The concentration is 4.9g/L, Na+Has a concentration of 0.95g/L, Mg2+、Ca2+The total concentration of (2) was 0.7 g/L.
Example 8
This embodiment is different from embodiment 7 in that:
the molar ratio of calcium oxide to magnesium ions in the secondary rubidium-enriched liquid is 3:1, and the reaction temperature of precipitated magnesium is 100 ℃;
and (3) taking the obtained back-extraction four-stage rubidium-rich liquid, evaporating to dryness at 100 ℃, and drying at 160 ℃ to obtain a rubidium chloride product with the purity of 93.4 wt%.
Example 9
Rubidium chloride is extracted by taking potassium chloride products of certain salt lake enterprises as raw materials, wherein Rb in the potassium chloride products+0.0093% of the total weight of the alloy, 96.74 wt% of KCl and Mg2+The content is 0.13 wt%, and the sodium content is 0.3 wt%;
adding water 550g into the obtained potassium chloride 1000g, partially dissolving at 60 deg.C, the weight ratio of water amount and potassium chloride is 0.55:1, the dissolving temperature is 25 deg.C, filtering, the solid phase is high purity potassium chloride product 850g, and the liquid phase is first order rubidium-rich liquid 689g, wherein Rb is+The concentration is 73.80mg/L, K+The concentration is 86.4g/L, Mg2+The concentration is 2.31g/L, Na+The concentration is 1.9 g/L;
evaporating and concentrating 682g of the obtained first-stage rubidium-rich liquid at 25 deg.C, crystallizing to separate out potassium chloride, and simultaneously obtaining 30g of second-stage rubidium-rich liquid, wherein Rb is+The concentration is 1029mg/L, K+The concentration is 98g/L, Mg2+The concentration of Na is 57.7g/L+The concentration is 47.7 g/L;
adding 7.92g of 30 wt% sodium hydroxide solution into 30g of secondary rubidium-enriched liquid at 25 ℃, enabling the pH value of the liquid phase to reach 13, carrying out solid-liquid separation on the obtained mixed reactant, wherein the separated solid phase is 9.9g of magnesium hydroxide, and the separated liquid phase is 26.89g of alkaline tertiary rubidium-enriched liquid, wherein Rb is+The concentration is 907mg/L, K+The concentration is 85.6g/L, Mg2+The concentration is 0.6g/L, Na+The concentration is 42 g/L;
adding 45% t-BAMBP-sulfonated kerosene organic phase into the alkaline tertiary rubidium-enriched liquid according to the volume ratio of O/A of 4:1, and performing extraction treatment at 10 ℃ to form a loaded organic phase; then carrying out back extraction treatment at 20 ℃ by using 6mol/L hydrochloric acid according to the ratio of 50:1 to obtain back extraction four-stage rubidium-rich liquid, wherein Rb is+The concentration is 9.02g/L, K+The concentration is 0.45g/L, Na+Has a concentration of 0.5g/L, Mg2+、Ca2+The total concentration of (a) is 0.7 g/L;
and (3) evaporating the obtained four-stage rubidium-enriched liquid at 20 ℃, and drying the obtained rubidium salt crystal at 80 ℃ to obtain a rubidium salt product, wherein the product purity is 95.3%. When 1kg of rubidium chloride is extracted, the comprehensive cost is about 1000-2000 yuan. Therefore, the process has excellent cost advantage in the aspect of extracting rubidium from high-potassium magnesium chloride brine.
In addition, the inventors of the present invention have also made experiments with reference to the above examples and other raw materials, process operations and process conditions described in the present specification, for example, in the reaction of precipitating magnesium, potassium hydroxide, calcium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, etc. may be used as the basic substance, t-BAMBP-based extractants may be selected from 4-methyl-2 (α -methylbenzyl) phenol, 4-ethyl-2 (α -methylbenzyl) phenol, 4-isopropyl-2 (α -methylbenzyl) phenol, 4-sec-butyl-2 (α -methylbenzyl) phenol, 4-tert-butyl-2 (α -methylbenzyl) phenol, etc., sulfonated kerosene may be replaced with 120 # solvent oil, 160 # solvent oil, 200 # solvent oil, D70 special solvent oil, D80 special solvent oil, aviation kerosene, etc., the back extractant can also adopt formic acid, acetic acid, hydrobromic acid, carbonic acid, sulfuric acid and the like, and more ideal results are obtained.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A method for extracting rubidium from high-potassium magnesium chloride brine is characterized by comprising the following steps:
(1) crystallizing high-potassium magnesium chloride brine to form carnallite ore by brine blending and evaporation technologies, removing sodium chloride impurity minerals by using a flotation technology to obtain high-grade low-sodium carnallite, and then producing potassium chloride by using a carnallite cold decomposition method, wherein the grade of the potassium chloride is more than 90%, the sodium content is lower than 5 wt%, the magnesium content is lower than 5 wt%, and the water content is lower than 10 wt%;
(2) adding water into the potassium chloride obtained in the step (1) for partial dissolution at the temperature of 0-100 ℃, then carrying out solid-liquid separation to obtain a first-stage rubidium-rich liquid and potassium chloride, and drying the potassium chloride to obtain a fertilizer-grade product; wherein the concentration of rubidium ions in the first-stage rubidium-rich liquid is 30-100 mg/L, the concentration of potassium ions is 60-200 g/L, the concentration of sodium ions is 0.5-8 g/L, and the concentration of magnesium ions is 0.5-5 g/L;
(3) evaporating and concentrating the primary rubidium-rich liquid obtained in the step (2), crystallizing and precipitating potassium chloride with the purity of more than 99%, and performing solid-liquid separation to obtain a secondary rubidium-rich liquid, wherein the concentration of rubidium ions in the secondary rubidium-rich liquid is 500-2000 mg/L, the concentration of potassium ions is 80-200 g/L, the concentration of magnesium ions is 10-120 g/L, and the concentration of sodium ions is 20-100 g/L;
(4) adjusting the pH value of the secondary rubidium-rich liquid obtained in the step (3) to 8-14 by using an alkaline substance, and precipitating partial magnesium carbonate or magnesium hydroxide to obtain a primary tertiary rubidium-rich liquid, wherein the concentration of rubidium ions in the primary tertiary rubidium-rich liquid is 400-1800 mg/L, the concentration of potassium ions is 70-190 g/L, the concentration of magnesium ions is 0.5-10 g/L, and the concentration of sodium ions is 15-60 g/L, wherein the alkaline substance comprises a solid or solution of alkali metal or alkaline earth metal hydroxide or carbonate, the alkaline substance comprises any one or a combination of more than two of sodium hydroxide, potassium hydroxide, calcium oxide, sodium bicarbonate, sodium carbonate and potassium carbonate, and the reaction temperature for precipitating magnesium is 10-100 ℃;
(5) carrying out extraction and back extraction treatment on rubidium ions in the alkaline tertiary rubidium-rich liquid obtained in the step (4) by adopting an organic phase consisting of a t-BAMBP extractant and a diluent to obtain a back-extraction quaternary rubidium-rich liquid, wherein the concentration of the rubidium ions in the back-extraction quaternary rubidium-rich liquid is 2000-90000 mg/L, the concentration of potassium ions is lower than 5000mg/L, the concentration of sodium ions is lower than 1000mg/L, and the total concentration of magnesium and calcium ions is lower than 1000 mg/L;
(6) and (3) evaporating the back-extracted four-stage rubidium-enriched liquid obtained in the step (5) to crystallize and precipitate rubidium salt, so that rubidium is extracted, wherein the purity of the obtained product rubidium chloride is more than 90%, the potassium content is lower than 3 wt%, the sodium content is lower than 2 wt%, and the magnesium and calcium contents are lower than 1 wt%.
2. The method of claim 1, wherein: in the step (1), the concentration of potassium ions in the high-potassium magnesium chloride brine is more than 5g/L, the concentration of magnesium ions is more than 10g/L, and the concentration of rubidium ions is more than 5 mg/L.
3. The method of claim 1, wherein: in the step (2), the mass ratio of the added water to the potassium chloride is 0.5: 1-1.5: 1, and the dissolving temperature is 0-60 ℃; and/or in the step (2) and the step (3), the solid-liquid separation mode adopts filtration, sedimentation overflow or centrifugal separation.
4. The method of claim 1, wherein: in the step (3), the temperature of evaporation concentration is 0-110 ℃, and the concentration multiple is 5-50 times.
5. The method of claim 1, wherein: in the step (4), the molar ratio of the alkaline substance to the magnesium ions in the secondary rubidium-rich liquid is 1-3: 1, the reaction temperature for precipitating magnesium is 20-80 ℃.
6. The method of claim 1, wherein: in the step (5), the organic phase for extraction is formed by uniformly mixing 5-45% by volume of t-BAMBP extractant and 55-95% by volume of diluent; wherein the t-BAMBP extractant comprises any one or the combination of more than two of 4-methyl-2 (alpha-methylbenzyl) phenol, 4-ethyl-2 (alpha-methylbenzyl) phenol, 4-isopropyl-2 (alpha-methylbenzyl) phenol, 4-sec-butyl-2 (alpha-methylbenzyl) phenol and 4-tert-butyl-2 (alpha-methylbenzyl) phenol; preferably, the diluent comprises any one or the combination of more than two of No. 120 solvent naphtha, No. 160 solvent naphtha, No. 200 solvent naphtha, D70 special solvent naphtha, D80 special solvent naphtha, aviation kerosene and sulfonated kerosene; preferably, the volume ratio of the alkaline tertiary rubidium-rich liquid to the organic phase for extraction is 1: 4-4: 1.
7. The method of claim 1, wherein: in the step (5), the temperature of the extraction operation is 10-40 ℃.
8. The method according to claim 1, wherein in step (5), the stripping process comprises: carrying out back extraction treatment on the extracted system by using a mixture of an organic phase and a back extractant; preferably, the stripping agent comprises an acid aqueous solution with a molar concentration of 0.1-6.0 mol/L, and preferably comprises any one or a combination of more than two of formic acid, acetic acid, nitric acid, hydrochloric acid, hydrobromic acid, carbonic acid and sulfuric acid; preferably, the volume ratio of the organic phase to the stripping agent is 1: 1-50: 1.
9. The method of claim 1, wherein: in the step (6), the temperature of the evaporation treatment is 20-100 ℃.
10. The method according to claim 1, characterized in that step (6) comprises in particular: naturally evaporating the back-extracted four-stage rubidium-enriched liquid obtained in the step (5) or forcibly evaporating the back-extracted four-stage rubidium-enriched liquid by a multi-effect evaporator so as to crystallize and precipitate rubidium salt, and drying the obtained rubidium salt crystal to obtain a rubidium salt product; preferably, the drying temperature is 80-160 ℃.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528666A (en) * | 2003-10-08 | 2004-09-15 | 四川石油管理局川西北矿区 | Process for preparing kali salt and boric acid from bittern |
| CN101691239A (en) * | 2009-09-30 | 2010-04-07 | 达州市恒成能源（集团）有限责任公司 | Comprehensive utilization method for bittern |
| CN101966399A (en) * | 2010-09-08 | 2011-02-09 | 中国科学院青海盐湖研究所 | Synergic extractant for extracting rubidium salt from brine and extraction method thereof |
| CN101987733A (en) * | 2010-07-19 | 2011-03-23 | 江西赣锋锂业股份有限公司 | Method for separating potassium and rubidium from lepidolite processing fluid |
| US20140170041A1 (en) * | 2009-06-24 | 2014-06-19 | Simbol Inc | Methods for Removing Potassium, Rubidium, and Cesium, Selectively or in Combination, From Brines and Resulting Compositions Thereof |
| CN103882227A (en) * | 2014-04-04 | 2014-06-25 | 成都理工大学 | Novel rubidium-potassium separating extracting agent and separating method |
| CN104326496A (en) * | 2014-10-14 | 2015-02-04 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting rubidium salt from brine and method for extracting cesium salt from brine |
| CN104789800A (en) * | 2015-05-08 | 2015-07-22 | 中国科学院青海盐湖研究所 | Method for extracting rubidium from saline lake brine |
| CN105256150A (en) * | 2015-10-26 | 2016-01-20 | 中国科学院青海盐湖研究所 | Method for extracting rubdium and cesium from acid brine |
| CN107267777A (en) * | 2017-06-09 | 2017-10-20 | 北京矿冶研究总院 | Novel method for extracting rubidium from rubidium-containing ore |
| CN110550644A (en) * | 2019-10-08 | 2019-12-10 | 河北铸合集团兴隆县矿业有限公司 | method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite |
| WO2021118938A1 (en) * | 2019-12-13 | 2021-06-17 | Cytec Industries Inc. | Methods for recovering organic salts from industrial process streams |
-
2021
- 2021-06-22 CN CN202110690567.6A patent/CN113307299B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528666A (en) * | 2003-10-08 | 2004-09-15 | 四川石油管理局川西北矿区 | Process for preparing kali salt and boric acid from bittern |
| US20140170041A1 (en) * | 2009-06-24 | 2014-06-19 | Simbol Inc | Methods for Removing Potassium, Rubidium, and Cesium, Selectively or in Combination, From Brines and Resulting Compositions Thereof |
| CN101691239A (en) * | 2009-09-30 | 2010-04-07 | 达州市恒成能源（集团）有限责任公司 | Comprehensive utilization method for bittern |
| CN101987733A (en) * | 2010-07-19 | 2011-03-23 | 江西赣锋锂业股份有限公司 | Method for separating potassium and rubidium from lepidolite processing fluid |
| CN101966399A (en) * | 2010-09-08 | 2011-02-09 | 中国科学院青海盐湖研究所 | Synergic extractant for extracting rubidium salt from brine and extraction method thereof |
| CN103882227A (en) * | 2014-04-04 | 2014-06-25 | 成都理工大学 | Novel rubidium-potassium separating extracting agent and separating method |
| CN104326496A (en) * | 2014-10-14 | 2015-02-04 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting rubidium salt from brine and method for extracting cesium salt from brine |
| CN104789800A (en) * | 2015-05-08 | 2015-07-22 | 中国科学院青海盐湖研究所 | Method for extracting rubidium from saline lake brine |
| CN105256150A (en) * | 2015-10-26 | 2016-01-20 | 中国科学院青海盐湖研究所 | Method for extracting rubdium and cesium from acid brine |
| CN107267777A (en) * | 2017-06-09 | 2017-10-20 | 北京矿冶研究总院 | Novel method for extracting rubidium from rubidium-containing ore |
| CN110550644A (en) * | 2019-10-08 | 2019-12-10 | 河北铸合集团兴隆县矿业有限公司 | method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite |
| WO2021118938A1 (en) * | 2019-12-13 | 2021-06-17 | Cytec Industries Inc. | Methods for recovering organic salts from industrial process streams |
Non-Patent Citations (2)
| Title |
|---|
| NAN ZHANG,ET AL.: "Rubidium and Cesium Recovery from Brine Resources", 《ADVANCED MATERIALS RESEARCH》 * |
| 宝阿敏等: "铷、铯的分离提取方法及其研究进展", 《应用化工》 * |
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