CN113307299B - Method for extracting rubidium from high-potassium magnesium chloride brine - Google Patents
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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 adopting 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 of potassium ions by accurately controlling the partial dissolution-crystallization process of rubidium-containing saline 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 sources such as atomic clocks, catalysts, magnetofluids, thermionic power generation, photovoltaic cells and the like and high and new technology fields. 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, and the method is directly used in the actual production process of a system with trace rubidium and a large amount of potassium, magnesium, calcium and other impurities coexisting, so that the production cost is extremely high, and the economic requirement of products cannot be met. For example, chinese patent CN 1094332a discloses a method for enriching and extracting rubidium from brine, which uses copper nitrate and potassium ferricyanide to synthesize an ion exchanger, and is used for enriching and extracting rubidium from brine used in salt manufacturing enterprises before salt manufacturing, wherein the one-time adsorption rate is high, but the concentration of rubidium in eluent obtained by the method is low, the potassium content is still very high (the weight ratio of potassium to rubidium is-40). In addition, the weight ratio of potassium to rubidium in the rubidium extracting liquid applicable to the method is only 135.
Chinese patent CN 109824068A discloses a method for extracting Rb from low-concentration brine and preparing high-purity rubidium salt, wherein ammonium phosphomolybdate and ammonium phosphotungstate, polyvinyl alcohol, sodium alginate and sodium silicate are prepared into rubidium ion adsorption microspheres, and the rubidium ion adsorption microspheres are filled into an adsorption column and used for adsorbing rubidium ions from rubidium-containing brine, and ammonium salt solution is used for desorption to obtain rubidium-rich feed liquid. However, this patent does not disclose the concentration of potassium ions in the raw material solution, and merely states that the rubidium ion concentration needs to be 40mg/L or higher. In the literature, "research on extraction of rubidium ions from ammonium phosphomolybdate" (Cao Dongmei, salt industry and chemical industry, 2014, 43, 22-24.), it is clearly indicated that coexisting potassium ions have a significant negative effect on the adsorption effect of rubidium ions by an ammonium phosphomolybdate adsorbent, and when the potassium concentration is 0.8g/L and the rubidium concentration is 1.7g/L, the exchange capacity of ammonium phosphomolybdate for rubidium ions can be reduced by more than 10%, and in high-potassium-rubidium ratio brine (> 1000.
Chinese patent CN 86 101311A discloses a process for extracting rubidium and cesium from weathered shells of acid-alkali rock magma or ion-exchange type rare earth ores, which uses a bispicloram-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 weak in acidity. Furthermore, the method does not examine the effect of potassium on rubidium and cesium extraction and separation.
Chinese patent CN 101987733A discloses a method for separating potassium and rubidium from lepidolite treatment liquid, which adds high-concentration magnesium chloride into the lepidolite treatment liquid, separates potassium and rubidium from the solution in the form of carnallite, heats and dissolves the obtained potassium and rubidium carnallite crystal in water, adjusts the pH value to 11-13 by NaOH, and leads most of Mg to be Mg (OH) 2 Separating the precipitate to obtain a mother solution which is a mixed solution of potassium chloride and rubidium chloride. The method comprises the following steps: (1) almost all Mg needs to be replaced by Mg (OH) 2 The 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 and 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 t-BAMBP substituted phenol extraction agents, 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 CN104789800 a and CN 105256150A still have t-BAMBP substituted phenol extractant as the extraction system, and the problem of high rubidium extraction cost still exists when the extraction technology is used in high magnesium system, 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 107460344A discloses a new method for extracting rubidium from brine by using t-BAMBP extractant, and the alkali amount required for directly adjusting the pH of brine can be reduced 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 Jianfeng, 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 brine, and the extraction pretreatment cost of the step is still extremely high because the content of magnesium and calcium is higher by several orders of magnitude than that of rubidium and cesium. Patent CN 105664845A discloses an adsorbent for activating zeolite and ammonium phosphomolybdate, which is compatible with rubidium ion, 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 very high, and it is still a high energy consumption link no matter the subsequent concentration crystallization or separation of rubidium and ammonium. Patent CN 106145242A has developed a new cyclic ether extractant which can simultaneously separate potassium, rubidium, cesium and strontium ions from salt lake brine, but the separation capability of this method is poor, and even if these elements are simultaneously separated out of brine system, the subsequent separation for obtaining their respective corresponding products is still a problem. U.S. Pat. No. 7,323,150 B2 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 evaporation and 'ammonium burning' for each 1kg of rubidium chloride recovered 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 extractants which are most researched and most widely applied at present, has better rubidium and potassium separation capacity, 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, when the raw brine is used for the salt lake brine of Carer, the raw brine and the carnallite decomposition mother liquor are both near-neutral systems, and the rubidium concentration is extremely low (<50 Mg/L) and the Mg concentration is extremely high, 7000 and 1000 times the Rb concentration respectively. During the pretreatment process of adjusting pH before extraction, mg forms Mg (OH) 2 Or MgCO 3 Precipitation, consumption of large amount of NaOH or Na 2 CO 3 Therefore, the comprehensive cost is high; mg (OH) formed on the other hand 2 Or MgCO 3 The entrainment of the precipitation mother liquor is extremely large (40-80%), 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 5wt%, the magnesium content is lower than 5wt%, and the water content is lower than 10wt%;
(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-enriched 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 carrying out 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, 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 1000mg/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 3wt%, the sodium content is lower than 2wt%, and the magnesium and calcium contents are lower than 1wt%.
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 rubidium concentration in a liquid phase is increased from 10mg/l in salt lake brine to more than hundreds of mg/l, the material quantity 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 the embodiments 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 5wt%, the magnesium content is lower than 5wt%, and the water content is lower than 10wt%;
(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-enriched 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 carrying out 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, 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 1000mg/L;
(6) And (4) 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 3wt%, the sodium content is lower than 2wt%, and the magnesium and calcium contents are lower than 1wt%.
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 5 g/L), the concentration of magnesium ions is more than 10g/L (Mg) 2+ The concentration is more than or equal to 10 g/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 step (2), the mass ratio of the added water to the potassium chloride is 0.5 to 1.5.
Further, in the step (2) and the step (3), the solid-liquid separation manner is filtration, sedimentation overflow, centrifugal separation, or the like, but is not limited thereto.
In some embodiments, in step (3), the temperature of the evaporative concentration is 0 ℃ to 110 ℃, and the concentration multiple is 5 to 50.
In some embodiments, in step (4), the molar ratio of the basic substance to the magnesium ions in the secondary rubidium-rich liquid is 1 to 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 step (5), the organic phase for extraction is prepared 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 naphtha, 160 # solvent naphtha, 200 # solvent naphtha, D70 special solvent naphtha, D80 special solvent naphtha, 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 treatment comprises: and (4) carrying out back extraction treatment on the extracted system by using a mixture of an organic phase and a back extractant.
Further, 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, any one or a combination of two or more of formic acid, acetic acid, nitric acid, hydrochloric acid, hydrobromic acid, carbonic acid, sulfuric acid, and the like, 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.
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 potassium chloride in the rubidium-containing saline lake 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 subject matter set forth herein is limited to the examples set forth below. 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 and high potassium 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, mg 2+ Concentration of 46g/L, ca 2+ The concentration was 0.2g/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, mg 2+ The concentration of Ca is 106g/L 2+ Concentration of 0.57 g/L) is evaporated continuously, the brine is crystallized to form 5.73kg of carnallite ore with grade of 77%. Removing NaCl impurities in carnallite ores by flotation to obtain 4.42kg of carnallite with the grade of 99%, adding 2.07L of water into the carnallite to decompose and produce potassium chloride, and circularly decomposing mother liquor to obtain 1.01kg of potassium chloride; rb in the obtained potassium chloride + 0.025wt%, 0.53wt% sodium, 97wt% KCl, and Mg 2+ The content is 0.1wt%;
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, mg 2+ The concentration is 0.98g/L, na + The concentration is 5.2g/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, mg 2+ The concentration is 21.5g/L, na + The concentration was 46g/L. Adding 30wt% of oxyhydrogen into the secondary rubidium-enriched liquid according to 1.1 times of the amount of magnesium ion substances at room temperature6.4g of sodium hydroxide solution, the pH value of the liquid phase reaches 13.7, the reaction temperature of the precipitated magnesium is 40 ℃, the obtained mixed reactant is subjected to solid-liquid separation, the separated solid phase is 1.5g of magnesium hydroxide, and the separated liquid phase is 27g of alkaline tertiary rubidium-rich liquid, wherein Rb is Rb + The concentration is 772mg/L, K + The concentration is 101g/L, mg 2+ The concentration is 0.6g/L, na + The concentration is 39g/L;
adding 30% t-BAMBP-sulfonated kerosene organic phase to the alkaline tertiary rubidium-rich solution at a volume ratio O/a of 2:1, and performing extraction treatment at 20 ℃ to form a loaded organic phase; then carrying out stripping treatment at 20 ℃ by using 1mol/L HCl according to a phase ratio of 20 + The concentration is 7.7g/L, K + The concentration is 0.25g/L, na + Has a concentration of 0.9g/L, mg 2+ 、Ca 2+ The total concentration of (A) is 0.5g/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 with the purity of 95.02%.
Example 2
The present embodiment is different from embodiment 1 in that:
250g of the potassium chloride obtained in example 1, in which Rb is used + 0.025wt%, 0.53wt% sodium, 97wt% KCl, and Mg 2+ 0.1wt% of calcium, 0.14wt% 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, mg 2+ The concentration of Na is 0.94g/L + The concentration was 4.9g/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 + 0.025wt%, 0.53wt% sodium, 97wt% KCl, and Mg 2+ 0.1wt% of calcium, 0.14wt% of calcium, 375g of water, 100 ℃ for partial dissolution, 195g of high-purity potassium chloride product as a solid phase after filtration,the liquid phase is 155g of first-stage rubidium-rich liquid, wherein Rb is + The concentration is 88mg/L, K + The concentration is 198g/L, mg 2+ The concentration is 0.95g/L, na + The concentration was 5.1g/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, mg 2 + The concentration of Na is 0.94g/L + 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, mg 2+ The concentration is 11.75g/L, na + The concentration was 61g/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, mg 2 + 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, mg 2+ The concentration of the sodium hydroxide is 19g/L, na + The concentration was 58g/L.
Example 6
The present 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, mg 2 + The concentration is 19g/L, na + Adding calcium oxide 0.35g into the solution with a concentration of 58g/L, reacting at 25 deg.C to form magnesium carbonate precipitate, filtering the precipitate to obtain alkaline tertiary rubidium-rich solution 6.5g, wherein Rb is + The concentration is 1800mg/L, K + The concentration is 180g/L, mg 2+ The concentration is 0.6g/L, na + The concentration was 54g/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 O/A of 1:4, and performing extraction treatment at 40 ℃ to form a loaded organic phase; then performing 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, mg 2+ 、Ca 2+ The total concentration of (2) was 0.7g/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 93.4wt%.
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%, KCl 96.74wt%, mg 2+ The content is 0.13wt%, and the sodium content is 0.3wt%;
and (2) adding 550g of water into 1000g of the obtained potassium chloride, and partially dissolving at 60 ℃, wherein the weight ratio of the added water to the potassium chloride is 0.55 + The concentration is 73.80mg/L, K + The concentration is 86.4g/L, mg 2+ The concentration is 2.31g/L, na + The concentration is 1.9g/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, mg 2+ The concentration of Na is 57.7g/L + At a concentration of 47.7g/L；
Adding 7.92g of 30wt% sodium hydroxide solution into 30g of secondary rubidium-rich 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-rich liquid, wherein Rb is + The concentration is 907mg/L, K + The concentration is 85.6g/L, mg 2+ The concentration is 0.6g/L, na + The concentration is 42g/L;
adding 45% of t-BAMBP-sulfonated kerosene organic phase into the alkaline tertiary rubidium-rich liquid according to the volume ratio 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 a phase ratio of 50 + The concentration is 9.02g/L, K + The concentration is 0.45g/L, na + Has a concentration of 0.5g/L, mg 2+ 、Ca 2+ The total concentration of (b) is 0.7g/L;
and (3) evaporating the obtained quaternary rubidium-enriched liquid at 20 ℃, and drying the obtained rubidium salt crystal at 80 ℃ to obtain a rubidium salt product with the purity of 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 # mineral spirit, 160 # mineral spirit, 200 # mineral spirit, D70 specialty mineral spirit, D80 mineral spirit, aviation kerosene, etc., formic acid, acetic acid, hydrobromic acid, carbonic acid, sulfuric acid, etc. may be used as the stripping agent, and all the preferable 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 halogen 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 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, the concentration of rubidium ions is more than 5mg/L, the grade of potassium chloride is more than 90%, the sodium content is lower than 5wt%, the magnesium content is lower than 5wt%, and the water content is lower than 10wt%;
(2) Adding water into the potassium chloride obtained in the step (1) for partial dissolution, wherein the mass ratio of the added water to the potassium chloride is 0.5 to 1.5, the temperature is 0-60 ℃, 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 primary 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 temperature of evaporation and concentration is 0-110 ℃, the concentration multiple is 5-50 times, the concentration of rubidium ions in the secondary rubidium-rich liquid is 500 mg/L-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, precipitating partial magnesium carbonate or magnesium hydroxide, and obtaining a tertiary alkaline rubidium-rich liquid, wherein the molar ratio of the alkaline substance to magnesium ions in the secondary rubidium-rich liquid is 1~3:1, the reaction temperature of magnesium precipitation is 20-80 ℃, the concentration of rubidium ions in the alkaline tertiary rubidium-rich liquid is 400 mg/L-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 sodium hydroxide, potassium hydroxide, calcium oxide, sodium bicarbonate, sodium carbonate and potassium carbonate, and the reaction temperature of magnesium precipitation is 10-100 ℃;
(5) Performing 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, so as to obtain a back-extraction quaternary rubidium-rich liquid, wherein the volume ratio of the alkaline tertiary rubidium-rich liquid to the organic phase for extraction is 1;
(6) And (4) 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 3wt%, the sodium content is lower than 2wt%, and the magnesium and calcium contents are lower than 1wt%.
2. The method of claim 1, wherein: in the step (2) and the step (3), the solid-liquid separation mode adopts filtration, sedimentation overflow or centrifugal separation.
3. The method of claim 1, wherein: in the step (5), the organic phase for extraction is formed by uniformly mixing 5 to 45 volume percent of t-BAMBP extractant and 55 to 95 volume percent 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; 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.
4. The method of claim 1, wherein: in the step (5), the temperature of the extraction operation is 10-40 ℃.
5. The method according to claim 1, wherein 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.
6. The method of claim 5, wherein the stripping agent comprises an aqueous acid solution with a molar concentration of 0.1 to 6.0 mol/L.
7. The method of claim 6, wherein the stripping agent comprises an aqueous solution of any one or a combination of two or more of formic acid, acetic acid, nitric acid, hydrochloric acid, hydrobromic acid, carbonic acid, and sulfuric acid.
8. The method of claim 1, wherein: in the step (6), the temperature of the evaporation treatment is 20-100 ℃.
9. The method according to claim 1, wherein step (6) comprises in particular: and (4) carrying out natural evaporation or forced evaporation by a multi-effect evaporator on the back-extracted four-stage rubidium-enriched liquid obtained in the step (5), so that rubidium salt is crystallized and precipitated, and drying the obtained rubidium salt crystal to obtain a rubidium salt product.
10. The method of claim 9, wherein the drying temperature is 80 ℃ to 160 ℃.
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| CN101987733B (en) * | 2010-07-19 | 2012-07-11 | 江西赣锋锂业股份有限公司 | Method for separating potassium and rubidium from lepidolite processing fluid |
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