CN113584330A - From CO2+O2Method for comprehensively recovering rhenium from in-situ leaching uranium mining leachate - Google Patents

From CO2+O2Method for comprehensively recovering rhenium from in-situ leaching uranium mining leachate Download PDF

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CN113584330A
CN113584330A CN202011376515.3A CN202011376515A CN113584330A CN 113584330 A CN113584330 A CN 113584330A CN 202011376515 A CN202011376515 A CN 202011376515A CN 113584330 A CN113584330 A CN 113584330A
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rhenium
uranium
resin
extraction
leaching
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胥国龙
闻振乾
郑剑平
姚益轩
原渊
杜志明
张翀
王兴
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Beijing Research Institute of Chemical Engineering and Metallurgy of CNNC
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Beijing Research Institute of Chemical Engineering and Metallurgy of CNNC
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention belongs to the technical field of in-situ leaching uranium mining, and particularly relates to secondary CO2+O2The method for comprehensively recovering rhenium from the in-situ leaching uranium extraction leachate can be used for recovering rhenium in the uranium recovery process. By using strongly basic anion exchange resins for CO2+O2And (4) adsorbing the in-situ leaching uranium extraction leachate to realize the separation and enrichment of uranium and rhenium. The rhenium qualified liquid is extracted by adopting an amine extractant, so that the rhenium concentration in the solution is further improved, and finally, a rhenium product is prepared. By adopting the method, the rhenium concentration in the leaching solution can be increased by 30000The recovery rate of rhenium can reach more than 90 percent.

Description

From CO2+O2Method for comprehensively recovering rhenium from in-situ leaching uranium mining leachate
Technical Field
The invention belongs to the technical field of in-situ leaching uranium mining, and particularly relates to secondary CO2+O2A method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate.
Background
In recent years, under the background of the demand of improving the natural uranium capacity of China and guaranteeing the nuclear power development, the exploration and development of natural uranium is continuously increased, and a large number of locally leachable sandstone-type uranium deposits are discovered in regions such as Xinjiang and inner Mongolia in succession. According to the research data of geological departments, the sandstone-type uranium deposit contains a large amount of associated elements such as molybdenum, rare earth, selenium, rhenium, vanadium and the like besides uranium. Among them, rhenium is receiving more and more attention as a material in the modern high and new technology industry.
As the metal rhenium has the characteristics of wear resistance, corrosion resistance, high hardness, good ductility, strong catalytic activity and the like, the rhenium and the rhenium alloy are mainly applied to the fields of aerospace, nuclear energy, electronic industry, thermosensitive element manufacturing and the like. The abundance of rhenium in the earth crust is very low, the rhenium almost has no simple substance form, and is associated with minerals such as molybdenum, copper, uranium and the like and mainly dispersed in molybdenite and bornite. The worldwide rhenium detection reserves are about 2500t, concentrated in a few countries like chile, usa and russia. Rhenium resources in China are not abundant, and the reserve of the preserved resources is only 237 t. Therefore, the recovery of the rhenium associated with the sandstone-type uranium ores can meet part of the demands of rhenium in China.
Most of global rhenium manufacturers extract rhenium from roasting smoke dust and leacheate of molybdenite with high rhenium content, and some domestic manufacturers also extract rhenium from rhenium-containing molybdenum concentrate by adopting an oxygen pressure oxidation method, but transfer rhenium in a solid phase into a solution and then separate, enrich and recover rhenium in the solution. At present, the separation and enrichment of rhenium from the solution mainly comprises a solvent extraction method, an ion exchange method, a liquid membrane separation method, an electrodialysis method, a precipitation method, an activated carbon adsorption method and the like.
Aiming at an acid method ground leaching process adopting sulfuric acid solution as a leaching agent, a process for simultaneously extracting uranium and rhenium is researched and developed and applied. The technological process includes the common adsorption of uranium and rhenium and the subsequent selective desorption. Rhenium desorption using a catalyst containing 80-90g/L NO 3-and 4.0-4.5% HNO3And rhenium is further extracted from the leacheate. The extractant is trioctylamine, the diluent is kerosene, the phase-change agent is decanol, and the back-extraction agent is ammonia water. After two times of extraction, high-concentration rhenium solution is obtained, and finally the product NH4ReO is prepared4。
CO2+O2The in-situ leaching uranium mining technology is environment-friendly and is applied to a plurality of in-situ leaching uranium mining mines at home and abroad. By using CO2+O2In the process of in-situ leaching uranium mining, uranium and rhenium are leached simultaneously, and rhenium in the leaching solution is extracted as ReO4-in the form. Compared with acid leaching, CO is adopted2+O2The impurity ions in the leaching hydrometallurgy recovery system have few types and low concentration, and are more beneficial to the recovery of rhenium. However, the rhenium content in sandstone-type uranium ores is low, and the rhenium concentration in-situ leaching uranium leaching leachate is low, so that the recovery of rhenium is difficult. At present, domestic CO2+O2Rhenium in the leaching solution of the in-situ leaching uranium mining mine is not effectively recycled, so that the rhenium resource is greatly wasted.
Disclosure of Invention
In view of the above disadvantages, it is an object of the present invention to provide a process for the removal of CO from a substrate2+O2Method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate, from CO2+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is used for recovering rhenium in the uranium recovery process to achieve the aim of recovering CO2+O2The purpose of comprehensively recovering rhenium in the in-situ leaching uranium extraction leachate is achieved.
The technical scheme of the invention is as follows:
from CO2+O2A method for comprehensively recovering rhenium from in-situ leaching uranium leaching leachate comprises the steps of (9), (1) adsorbing uranium and rhenium in the leachate together;
mixing uranium and rhenium containing CO2+O2Introducing the in-situ leaching uranium leaching solution serving as an adsorption stock solution into an ion exchange tower according to certain contact time, and jointly adsorbing uranium and rhenium in the leaching solution by using anion exchange resin; stopping adsorption when the concentration of uranium in the tail adsorption solution is basically the same as that of uranium in the raw adsorption solution, and at the moment, saturating the uranium on the resin;
(2) leaching uranium in the resin;
leaching uranium from the uranium saturated resin obtained in the step (1); introducing a uranium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified uranium liquid and rhenium-loaded resin; in the process, uranium on the resin is leached, rhenium is not leached, and the qualified uranium liquid is used for preparing a uranium product;
(3) transformation of rhenium-carrying resin;
transforming the rhenium-loaded resin in the step (2), and introducing a certain volume of the adsorption tail liquid in the step (1) to obtain a transformed rhenium-loaded resin;
(4) re-adsorption of uranium and rhenium;
repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3) until the concentration of rhenium in the tail liquid of the adsorption is basically the same as that of rhenium in the raw liquid of the adsorption, and stopping the adsorption, wherein the rhenium on the resin is saturated; performing the step (2) on the resin, and washing a uranium eluting agent among the resins by using clear water to obtain rhenium saturated resin;
(5) carrying out rhenium saturated resin pretreatment;
discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower into a tank, adding a hydrochloric acid solution according to a certain proportion to enable HCO adsorbed on the resin3 -And CO3 2-Fully reacting with acid until no bubbles are generated; loading the treated rhenium saturated resin into an ion exchange tower;
(6) leaching rhenium in the resin;
leaching rhenium on the treated rhenium saturated resin obtained in the step (5); introducing the rhenium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified rhenium liquid and rhenium-poor resin;
(7) transformation of the rhenium-poor resin;
transforming the rhenium-poor resin in the step (6), introducing a certain volume of clear water, washing a rhenium eluting agent among the resins, introducing a certain volume of the adsorption tail liquid in the step (1), finally obtaining the transformed rhenium-poor resin, and returning to the step (1) for continuous adsorption;
(8) extracting qualified rhenium liquid;
extracting rhenium from the qualified rhenium liquid obtained in the step (6); the extractant is amine extractant N235, the phase modifier is octanol, and the diluent is sulfonated kerosene; extracting rhenium in an extraction mixer-settler according to certain conditions to obtain a loaded organic phase;
(9) carrying out organic reverse extraction;
performing re-extraction on the rhenium according to the loaded organic phase obtained in the step (8); washing the loaded organic phase with clear water, performing back extraction by using a NaOH solution with a certain concentration, and returning the poor organic phase to the step (8) for continuous extraction to finally obtain a back extraction solution;
(10) preparing a rhenium product;
heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
The anion exchange resin in the step (1) is strong-base anion exchange resin D261; the contact time of the adsorption in the step (1) is 5min-10 min.
In the step (2), the NaCl concentration in the uranium eluting agent is 50g/L-100g/L, and NaHCO is used3The concentration is 5g/L-20g/L, the uranium leaching contact time is 45mi-60min, and the leaching volume is 6BV-10 BV.
The volume of the tail adsorption solution introduced in the step (3) is 2BV-5BV, so that Cl in the transformation solution-<1g/L。
In the step (5), the concentration of HCl is 10g/L-20g/L, the volume ratio of HCl solution to resin is 1/2-2/1, and the soaking time is 6h-24 h.
And (3) in the step (6), the rhenium eluting agent is 6-8 mol/L HCl solution, the rhenium eluting contact time is 45-120 min, and the eluting volume is 10-30 BV.
The volume of the clear water introduced in the step (7) is 3BV-6BV, pH of washing water>1.5, the volume of the introduced adsorption tail liquid is 2BV-5BV, so that Cl in the transformation liquid-<1g/L。
In the step (8), the volume fraction of the extracting agent N235 is 3-10%, the volume fraction of the phase modifier sec-octanol is 1-5%, the oil-water flow ratio O/A is 1/5-1/30, the extraction stage number is 3-6, and the single-stage extraction time is 1-5 min.
In the step (9), the flow ratio O/A of the loaded organic phase to the clean water is 1/1-1/2, the washing grade is 1-2 grade, and the washing time is 2min-5 min.
In the step (9), the concentration of the back-extraction agent NaOH is 0.5-4 mol/L, the flow ratio O/A of the loaded organic phase to the back-extraction agent is 5/1-40/1, the number of back-extraction stages is 1-2 stages, and the back-extraction time is 1-5 min.
The invention has the beneficial effects that:
by using strongly basic anion exchange resins for CO2+O2And (4) adsorbing the in-situ leaching uranium extraction leachate to realize the separation and enrichment of uranium and rhenium. The rhenium qualified liquid is extracted by adopting an amine extractant, so that the rhenium concentration in the solution is further improved, and finally, a rhenium product is prepared. By adopting the method, the concentration of rhenium in the leaching solution can be improved by more than 30000 times, and the recovery rate of rhenium can reach more than 90%.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
From CO2+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate comprises the following steps:
(1) the uranium and rhenium in the leaching solution are jointly adsorbed
Mixing uranium and rhenium containing CO2+O2And introducing the in-situ leaching uranium leaching liquid serving as an adsorption stock solution into an ion exchange tower according to a certain contact time, and jointly adsorbing uranium and rhenium in the leaching liquid by using anion exchange resin. And when the concentration of the uranium in the tail adsorption solution is basically the same as that of the uranium in the raw adsorption solution, stopping adsorption, and at the moment, saturating the uranium on the resin.
(2) Leaching of uranium in resins
And (3) leaching the uranium saturated resin obtained in the step (1) with uranium. And introducing the uranium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified uranium liquid and rhenium-loaded resin. In the process, uranium on the resin is leached, rhenium is not leached, and the qualified uranium liquid is used for preparing a uranium product.
(3) Transformation of rhenium-loaded resins
And (3) transforming the rhenium-loaded resin in the step (2), and introducing a certain volume of the adsorption tail liquid in the step (1) to obtain the transformed rhenium-loaded resin.
(4) Re-adsorption of uranium and rhenium
And (3) repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3) until the concentration of rhenium in the tail liquid of the adsorption is basically the same as that in the original liquid of the adsorption, stopping the adsorption, and at the moment, the rhenium on the resin is saturated. And (3) performing the step (2) on the resin, and washing the uranium eluting agent among the resins by using clear water to obtain the rhenium saturated resin.
(5) Rhenium saturated resin pretreatment
Discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower into a tank, adding a hydrochloric acid solution according to a certain proportion to enable HCO adsorbed on the resin3 -And CO3 2-React well with the acid until no more bubbles are formed. The treated rhenium saturated resin is loaded into an ion exchange column.
(6) Leaching of rhenium in resins
And (5) leaching rhenium on the treated rhenium saturated resin obtained in the step (5). And introducing the rhenium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified rhenium liquid and rhenium-poor resin.
(7) Transformation of rhenium-poor resins
And (3) transforming the rhenium-poor resin in the step (6), introducing a certain volume of clear water, washing a rhenium eluting agent among the resins, introducing a certain volume of the adsorption tail liquid in the step (1), finally obtaining the transformed rhenium-poor resin, and returning to the step (1) for continuous adsorption.
(8) Qualified rhenium liquid extraction
And (4) extracting rhenium from the qualified rhenium liquid obtained in the step (6). The extractant is amine extractant N235, the phase modifier is octanol, and the diluent is sulfonated kerosene. Rhenium is extracted in an extraction mixer-settler according to certain conditions to obtain a loaded organic phase.
(9) Loaded organic counter-extraction
And (4) performing re-extraction on the loaded organic phase obtained in the step (8). And (3) washing the loaded organic phase with clear water, performing back extraction by using a NaOH solution with a certain concentration, and returning the poor organic phase to the step (8) for continuous extraction to finally obtain a back extraction solution.
(10) Rhenium product preparation
Heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
The anion exchange resin in the step (1) is strong-base anion exchange resin D261.
The contact time of the adsorption in the step (1) is 5min-10 min.
In the step (2), the NaCl concentration in the uranium eluting agent is 50g/L-100g/L, and NaHCO is used3The concentration is 5g/L-20g/L, the uranium leaching contact time is 45mi-60min, and the leaching volume is 6BV-10 BV.
The volume of the tail adsorption solution introduced in the step (3) is 2BV-5BV, so that Cl in the transformation solution-<1g/L。
In the step (5), the concentration of HCl is 10g/L-20g/L, the volume ratio of HCl solution to resin is 1/2-2/1, and the soaking time is 6h-24 h.
And (3) in the step (6), the rhenium eluting agent is 6-8 mol/L HCl solution, the rhenium eluting contact time is 45-120 min, and the eluting volume is 10-30 BV.
The clear water introduced in the step (7)Accumulating at 3-6 BV to make the pH of the washing water>1.5, the volume of the introduced adsorption tail liquid is 2BV-5BV, so that Cl in the transformation liquid-<1g/L。
In the step (8), the volume fraction of the extracting agent N235 is 3-10%, the volume fraction of the phase modifier sec-octanol is 1-5%, the oil-water flow ratio O/A is 1/5-1/30, the extraction stage number is 3-6, and the single-stage extraction time is 1-5 min.
In the step (9), the flow ratio O/A of the loaded organic phase to the clean water is 1/1-1/2, the washing grade is 1-2 grade, and the washing time is 2min-5 min.
In the step (9), the concentration of the back-extraction agent NaOH is 0.5-4 mol/L, the flow ratio O/A of the loaded organic phase to the back-extraction agent is 5/1-40/1, the number of back-extraction stages is 1-2 stages, and the back-extraction time is 1-5 min.
Example 1:
(1) the uranium and rhenium in the leaching solution are jointly adsorbed
CO in certain place2+O2In the in-situ leaching uranium leaching leachate, the uranium concentration is 30mg/L, the rhenium concentration is 80 mug/L, the D261 resin is used for jointly adsorbing the uranium and the rhenium in the leachate, and the adsorption contact time is 5 min. And when the concentration of uranium in the tail liquid of the adsorption is more than 29mg/L, obtaining the uranium saturated resin.
(2) Leaching of uranium in resins
And (3) leaching the uranium saturated resin obtained in the step (1) with uranium. NaCl concentration in uranium leaching is 75g/L, NaHCO3The concentration is 10g/L, the uranium leaching contact time is 60min, and the leaching volume is 8V. The obtained qualified uranium liquid has the concentration of 21g/L and is used for preparing uranium products.
(3) Transformation of rhenium-loaded resins
Transforming the rhenium-carrying resin in the step (2), introducing 3BV of the adsorption tail liquid in the step (1), and adding Cl in the transformation liquid-The concentration was reduced to 0.4g/L to obtain a transformed rhenium-carrying resin.
(4) Re-adsorption of uranium and rhenium
And (4) repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3), wherein the rhenium on the resin is saturated through 8 cycles. And (3) performing the step (2) on the resin, and washing the uranium eluting agent in the resin by using 2BV clear water to obtain the rhenium saturated resin.
(5) Rhenium saturated resin pretreatment
Discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower to a tank, adding 10g/L HCl solution according to the volume ratio of the solution to the resin of 1/1, and soaking for 24 h. The treated rhenium saturated resin is loaded into an ion exchange column.
(6) Leaching of rhenium in resins
And (5) leaching rhenium on the treated rhenium saturated resin obtained in the step (5). The rhenium eluting agent is 6mol/L HCl solution, the rhenium eluting contact time is 60min, the eluting volume is 30BV, the eluting rate of rhenium in the resin is 99.2 percent, and the concentration of the obtained qualified rhenium solution is 42 mg/L.
(7) Transformation of rhenium-poor resins
Transforming the rhenium-depleted resin in step (6). Introducing 3BV of clear water, washing rhenium eluting agent among the resins, increasing the pH value of the washing water to 1.7, introducing 3BV of adsorption tail liquid in the step (1), and introducing Cl in the transformation liquid-The concentration was reduced to 0.6 g/L. Finally, the transformed rhenium-poor resin is returned to the step (1) to be continuously used for adsorption.
(8) Qualified rhenium liquid extraction
And (4) extracting rhenium from the qualified rhenium liquid obtained in the step (6). The extractant is 5 percent of N235, 1.5 percent of secondary octanol and 93.5 percent of sulfonated kerosene, the oil-water flow ratio O/A is 1/10, the extraction stage number is 4, the single-stage extraction time is 5min, the rhenium concentration in the final loaded organic phase is 395mg/L, the rhenium concentration in the raffinate water is less than 1mg/L, and the extraction rate of rhenium is 99.1 percent.
(9) Loaded organic counter-extraction
And (4) performing re-extraction on the loaded organic phase obtained in the step (8). Washing the loaded organic phase, wherein the flow ratio O/A of the loaded organic phase to clear water is 1/1, the washing grade is 2 grades, and the washing time is 3 min. And then carrying out back extraction by using a 1mol/L NaOH solution, wherein the flow ratio O/A of the loaded organic phase and the back extractant is 10/1, the number of back extraction stages is 2, and the back extraction time is 5 min. The concentration of the strip liquor is 3.9g/L, the rhenium concentration in the poor organic phase is 2mg/L, and the rhenium back-extraction rate is 99.5%. And (5) returning the poor organic phase to the step (8) for extraction, and finally obtaining the strip liquor.
(10) Rhenium product preparation
Heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
Example 2:
(1) the uranium and rhenium in the leaching solution are jointly adsorbed
CO in certain place2+O2In the in-situ leaching uranium leaching leachate, the uranium concentration is 22mg/L, the rhenium concentration is 0.1mg/L, the D261 resin is used for jointly adsorbing the uranium and the rhenium in the leachate, and the adsorption contact time is 7 min. And when the concentration of uranium in the adsorption tail liquid is more than 21mg/L, obtaining the uranium saturated resin.
(2) Leaching of uranium in resins
And (3) leaching the uranium saturated resin obtained in the step (1) with uranium. NaCl concentration in uranium leaching is 60g/L, NaHCO3The concentration is 15g/L, the uranium leaching contact time is 60min, and the leaching volume is 9V. The obtained qualified uranium liquid has a concentration of 14g/L and is used for preparing uranium products.
(3) Transformation of rhenium-loaded resins
Transforming the rhenium-carrying resin in the step (2), introducing 4BV of the adsorption tail liquid in the step (1), and adding Cl in the transformation liquid-The concentration was reduced to 0.2g/L to obtain a transformed rhenium-carrying resin.
(4) Re-adsorption of uranium and rhenium
And (4) repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3), wherein the rhenium on the resin is saturated after 6 cycles. And (3) carrying out the step (2) on the resin, and washing the uranium eluting agent in the resin by using 3BV clear water to obtain the rhenium saturated resin.
(5) Rhenium saturated resin pretreatment
Discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower to a tank, adding 20g/L HCl solution according to the volume ratio of the solution to the resin of 1/2, and soaking for 12 h. The treated rhenium saturated resin is loaded into an ion exchange column.
(6) Leaching of rhenium in resins
And (5) leaching rhenium on the treated rhenium saturated resin obtained in the step (5). The rhenium eluting agent is 7mol/L HCl solution, the rhenium eluting contact time is 45min, the eluting volume is 20BV, the eluting rate of rhenium in the resin is 98.1%, and the concentration of the obtained qualified rhenium solution is 74 mg/L.
(7) Transformation of rhenium-poor resins
Transforming the rhenium-depleted resin in step (6). Introducing clean water of 4BV, washing rhenium eluting agent among the resins, raising the pH value of the washing water to 1.6, introducing adsorption tail liquid in the step (1) of 3BV volume, and Cl in the transformation liquid-The concentration was reduced to 0.8 g/L. Finally, the transformed rhenium-poor resin is returned to the step (1) to be continuously used for adsorption.
(8) Qualified rhenium liquid extraction
And (4) extracting rhenium from the qualified rhenium liquid obtained in the step (6). The extraction agent is 6% of N235, 2% of secondary octanol and 92% of sulfonated kerosene, the oil-water flow ratio O/A is 1/12, the extraction stage number is 5, the single-stage extraction time is 5min, the rhenium concentration in the final loaded organic phase is 880mg/L, the rhenium concentration in the raffinate water is less than 1mg/L, and the extraction rate of rhenium is 98.9%.
(9) Loaded organic counter-extraction
And (4) performing re-extraction on the loaded organic phase obtained in the step (8). Washing the loaded organic phase, wherein the flow ratio O/A of the loaded organic phase to clear water is 1/2, the washing grade is 1 grade, and the washing time is 5 min. And then, carrying out back extraction by using a 2mol/L NaOH solution, wherein the flow ratio O/A of the loaded organic phase and the back extractant is 15/1, the number of back extraction stages is 1, and the back extraction time is 5 min. The concentration of the strip liquor is 13.1g/L, the rhenium concentration in the poor organic phase is 6mg/L, and the rhenium back-extraction rate is 99.3 percent. And (5) returning the poor organic phase to the step (8) for extraction, and finally obtaining the strip liquor.
(10) Rhenium product preparation
Heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
Example 3:
(1) the uranium and rhenium in the leaching solution are jointly adsorbed
CO in certain place2+O2In the in-situ leaching uranium leaching leachate, the uranium concentration is 17mg/L, the rhenium concentration is 60 mu g/L, the D261 resin is used for jointly adsorbing the uranium and the rhenium in the leachate, and the adsorption contact time is 5 min.And when the concentration of uranium in the tail liquid of the adsorption is more than 16mg/L, obtaining the uranium saturated resin.
(2) Leaching of uranium in resins
And (3) leaching the uranium saturated resin obtained in the step (1) with uranium. NaCl concentration in uranium leaching is 80g/L, NaHCO3The concentration is 12g/L, the uranium leaching contact time is 50min, and the leaching volume is 7V. The obtained qualified uranium liquid has the concentration of 11g/L and is used for preparing uranium products.
(3) Transformation of rhenium-loaded resins
Transforming the rhenium-carrying resin in the step (2), introducing 2BV of the adsorption tail liquid in the step (1), and adding Cl in the transformation liquid-The concentration was reduced to 0.9g/L to obtain a transformed rhenium-carrying resin.
(4) Re-adsorption of uranium and rhenium
And (4) repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3), wherein the rhenium on the resin is saturated after 7 cycles. And (3) carrying out the step (2) on the resin, and washing the uranium eluting agent in the resin by using 3BV clear water to obtain the rhenium saturated resin.
(5) Rhenium saturated resin pretreatment
Discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower to a tank, adding 10g/L HCl solution according to the volume ratio of the solution to the resin of 2/1, and soaking for 6 h. The treated rhenium saturated resin is loaded into an ion exchange column.
(6) Leaching of rhenium in resins
And (5) leaching rhenium on the treated rhenium saturated resin obtained in the step (5). The rhenium eluting agent is 8mol/L HCl solution, the rhenium eluting contact time is 45min, the eluting volume is 12BV, the rhenium eluting rate in the resin is 99.2 percent, and the obtained qualified rhenium solution has the concentration of 51 mg/L.
(7) Transformation of rhenium-poor resins
Transforming the rhenium-depleted resin in step (6). Introducing clear water of 6BV, washing rhenium eluting agent among the resins, raising the pH value of the washing water to 1.8, introducing adsorption tail liquid in the step (1) of 5BV volume, and introducing Cl in the transformation liquid-The concentration was reduced to 0.2 g/L. Finally, the transformed rhenium-poor resin is returned to the step (1) to be continuously used for adsorption.
(8) Qualified rhenium liquid extraction
And (4) extracting rhenium from the qualified rhenium liquid obtained in the step (6). The extraction agent is 8% of N235, 2% of secondary octanol and 90% of sulfonated kerosene, the oil-water flow ratio O/A is 1/10, the extraction stage number is 5, the single-stage extraction time is 4min, the rhenium concentration in the final loaded organic phase is 490mg/L, the rhenium concentration in the raffinate water is 2mg/L, and the extraction rate of rhenium is 96.1%.
(9) Loaded organic counter-extraction
And (4) performing re-extraction on the loaded organic phase obtained in the step (8). Washing the loaded organic phase, wherein the flow ratio O/A of the loaded organic phase to clear water is 1/2, the washing grade is 2 grades, and the washing time is 5 min. And then, carrying out back extraction by using 2.5mol/L NaOH solution, wherein the flow ratio O/A of the loaded organic phase and the back extractant is 10/1, the number of back extraction stages is 1, and the back extraction time is 3 min. The concentration of the strip liquor is 4.8g/L, the rhenium concentration in the poor organic phase is 9mg/L, and the rhenium back-extraction rate is 98.2%. And (5) returning the poor organic phase to the step (8) for extraction, and finally obtaining the strip liquor.
(10) Rhenium product preparation
Heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
In the drawings of the disclosed embodiments of the invention, only methods related to the disclosed embodiments are referred to, other methods can refer to common design, and the same embodiment and different embodiments of the invention can be combined with each other without conflict;
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.

Claims (10)

1. From CO2+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate comprises 9 steps, and is characterized in that:
(1) adsorbing uranium and rhenium in the leachate together;
mixing uranium and rhenium containing CO2+O2Introducing the in-situ leaching uranium leaching solution serving as an adsorption stock solution into an ion exchange tower according to certain contact time, and jointly adsorbing uranium and rhenium in the leaching solution by using anion exchange resin; stopping adsorption when the concentration of uranium in the tail adsorption solution is basically the same as that of uranium in the raw adsorption solution, and at the moment, saturating the uranium on the resin;
(2) leaching uranium in the resin;
leaching uranium from the uranium saturated resin obtained in the step (1); introducing a uranium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified uranium liquid and rhenium-loaded resin; in the process, uranium on the resin is leached, rhenium is not leached, and the qualified uranium liquid is used for preparing a uranium product;
(3) transformation of rhenium-carrying resin;
transforming the rhenium-loaded resin in the step (2), and introducing a certain volume of the adsorption tail liquid in the step (1) to obtain a transformed rhenium-loaded resin;
(4) re-adsorption of uranium and rhenium;
repeating the steps (1) to (3) on the transformed rhenium-carrying resin obtained in the step (3) until the concentration of rhenium in the tail liquid of the adsorption is basically the same as that of rhenium in the raw liquid of the adsorption, and stopping the adsorption, wherein the rhenium on the resin is saturated; performing the step (2) on the resin, and washing a uranium eluting agent among the resins by using clear water to obtain rhenium saturated resin;
(5) carrying out rhenium saturated resin pretreatment;
discharging the rhenium saturated resin obtained in the step (4) from the ion exchange tower into a tank, adding a hydrochloric acid solution according to a certain proportion to enable HCO adsorbed on the resin3 -And CO3 2-Fully reacting with acid until no bubbles are generated; loading the treated rhenium saturated resin into an ion exchange tower;
(6) leaching rhenium in the resin;
leaching rhenium on the treated rhenium saturated resin obtained in the step (5); introducing the rhenium eluting agent into an ion exchange tower according to a certain contact time, and eluting for a certain volume to obtain qualified rhenium liquid and rhenium-poor resin;
(7) transformation of the rhenium-poor resin;
transforming the rhenium-poor resin in the step (6), introducing a certain volume of clear water, washing a rhenium eluting agent among the resins, introducing a certain volume of the adsorption tail liquid in the step (1), finally obtaining the transformed rhenium-poor resin, and returning to the step (1) for continuous adsorption;
(8) extracting qualified rhenium liquid;
extracting rhenium from the qualified rhenium liquid obtained in the step (6); the extractant is amine extractant N235, the phase modifier is octanol, and the diluent is sulfonated kerosene; extracting rhenium in an extraction mixer-settler according to certain conditions to obtain a loaded organic phase;
(9) carrying out organic reverse extraction;
performing re-extraction on the rhenium according to the loaded organic phase obtained in the step (8); washing the loaded organic phase with clear water, performing back extraction by using a NaOH solution with a certain concentration, and returning the poor organic phase to the step (8) for continuous extraction to finally obtain a back extraction solution;
(10) preparing a rhenium product;
heating and evaporating the back extraction solution obtained in the step (9) until the volume of the liquid phase becomes smaller, adding saturated KCl solution, freezing and crystallizing at low temperature, and finally preparing KReO4And (5) producing the product.
2. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: the anion exchange resin in the step (1) is strong-base anion exchange resin D261; the contact time of the adsorption in the step (1) is 5min-10 min.
3. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: in the step (2), the NaCl concentration in the uranium eluting agent is 50g/L-100g/L, and NaHCO is used3The concentration is 5g/L-20g/L, the uranium leaching contact time is 45mi-60min, and the leaching volume is 6BV-10 BV.
4. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: the volume of the tail adsorption solution introduced in the step (3) is 2BV-5BV, so that Cl in the transformation solution-<1g/L。
5. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: in the step (5), the concentration of HCl is 10g/L-20g/L, the volume ratio of HCl solution to resin is 1/2-2/1, and the soaking time is 6h-24 h.
6. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: and (3) in the step (6), the rhenium eluting agent is 6-8 mol/L HCl solution, the rhenium eluting contact time is 45-120 min, and the eluting volume is 10-30 BV.
7. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: the volume of the clear water introduced in the step (7) is 3BV-6BV, so that the pH value of the washing water is adjusted>1.5, the volume of the introduced adsorption tail liquid is 2BV-5BV, so that Cl in the transformation liquid-<1g/L。
8. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: in the step (8), the volume fraction of the extracting agent N235 is 3-10%, the volume fraction of the phase modifier sec-octanol is 1-5%, the oil-water flow ratio O/A is 1/5-1/30, the extraction stage number is 3-6, and the single-stage extraction time is 1-5 min.
9. A secondary CO as claimed in claim 12+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: in the step (9), the flow ratio O/A of the loaded organic phase to the clean water is 1/1-1/2, the washing grade is 1-2 grade, and the washing time is 2min-5 min.
10. A secondary CO as claimed in claim 92+O2The method for comprehensively recovering rhenium from in-situ leaching uranium extraction leachate is characterized by comprising the following steps of: in the step (9), the concentration of the back-extraction agent NaOH is 0.5-4 mol/L, the flow ratio O/A of the loaded organic phase to the back-extraction agent is 5/1-40/1, the number of back-extraction stages is 1-2 stages, and the back-extraction time is 1-5 min.
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