CN117587277A - Method for preparing uranate by fractional precipitation - Google Patents

Method for preparing uranate by fractional precipitation Download PDF

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CN117587277A
CN117587277A CN202311510510.9A CN202311510510A CN117587277A CN 117587277 A CN117587277 A CN 117587277A CN 202311510510 A CN202311510510 A CN 202311510510A CN 117587277 A CN117587277 A CN 117587277A
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uranium
diuranate
solution
reaction
filtering
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苏学斌
王超
刘浩
支梅峰
蒋敏
何峰
王灵璞
谭国强
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Henan Zhonghe Jinyuan New Material Co ltd
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Henan Zhonghe Jinyuan New Material Co ltd
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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
    • 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
    • C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
    • C22B60/023—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors halogenated ion as active agent
    • 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
    • C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0247—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using basic solutions or liquors
    • 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
    • C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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

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Abstract

The invention discloses a method for preparing uranate by fractional precipitation, which comprises the following steps: step 1, dissolving unqualified diuranate with hydrochloric acid, and then filtering to obtain an acid solution; step 2, heating the acid solution, adding a neutralizing precipitant and hydrogen peroxide, controlling the reaction temperature and the pH value, and then aging and filtering to obtain uranium purified solution and iron-removing slag; step 3, adding sodium hydroxide solution into the uranium purified solution, and then aging and filtering to obtain qualified sodium diuranate; step 4, adding carbonate solution into the iron-removing slag, controlling the reaction liquid-solid ratio, the reaction temperature and the pH value, and then filtering to obtain uranium alkaline leaching solution; and 5, adding sodium hydroxide solution into the uranium alkaline leaching solution, and then aging and filtering to obtain qualified sodium diuranate. The invention aims to continuously extract qualified transuranate from unqualified transuranate so as to improve the recycling rate.

Description

Method for preparing uranate by fractional precipitation
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for preparing uranate by fractional precipitation.
Background
At present, uranium belongs to national strategic resources, and the existing uranium ore resources in China are very deficient. As nuclear power is increasingly paid attention to as clean energy, and the current situation of uranium ore resource shortage is faced, the technology for extracting uranium from unconventional uranium resources is paid attention to, in the hydrometallurgical process of co-associated uranium resources, radionuclide uranium is enriched to obtain a certain amount of disqualified products of transuranate, the content of iron in the disqualified products of transuranate is higher, and the mass fraction U of uranium is: 30% -45%, and Fe:5% -15%. And further, research on uranium extraction technology from unconventional uranium resources is developed, recycling of uranium resources is achieved, and the method has good industrial value.
The invention patent with the prior patent publication number of CN115896492A discloses a uranium beryllium separation and extraction method in uranium beryllium leaching solution, which discloses that uranium beryllium is thoroughly separated and purified, the recovery rate of uranium beryllium is high, the two leaching processes in the original uranium-beryllium leaching process are reduced, the flow is simplified, and valuable metals can be fully recovered. The invention patent with the prior patent publication number of CN111945001A discloses a method for treating monazite euthanasia slag, and discloses that iron and uranium separation adopts an extraction mode; however, the separation of uranium from other metals has not been disclosed for solving the problem of continuous recycling of transuranate reject.
Disclosure of Invention
The invention mainly aims to provide a method for preparing uranate by fractional precipitation, which aims to solve the technical problem that the existing disqualified uranate cannot efficiently recover uranium.
To achieve the above object, the present invention provides a method for preparing a diuranate by fractional precipitation, the method comprising the steps of:
step 1, dissolving unqualified diuranate with hydrochloric acid, and then filtering to obtain an acid solution;
step 2, heating the acid solution, adding a preset amount of neutralizing precipitant and hydrogen peroxide, controlling the reaction temperature and the pH value, and then aging and filtering to obtain uranium purified solution and iron-removing slag; wherein the reaction temperature is 85-90 ℃, and the pH value of the reaction end point is 3.2-3.5;
step 3, adding a preset amount of sodium hydroxide solution into the uranium purified solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate;
step 4, adding a preset amount of carbonate solution into the iron-removing slag, controlling the reaction liquid-solid ratio, the reaction temperature and the pH value, and then filtering to obtain uranium alkaline leaching solution;
and 5, adding a preset amount of sodium hydroxide solution into the uranium alkaline leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
Optionally, in step 1, the acid dissolution reaction liquid-solid ratio is (1.5-2.0) mL:1g, the reaction time is 1H-1.5H, and the residual H+ concentration is 0.25 mol/L-0.50 mol/L.
Optionally, in step 2, the neutralizing precipitant is a sodium hydroxide solution with a mass fraction of 30% or more; the mass fraction of the hydrogen peroxide is less than 3%.
Optionally, in step 2, the aging time is 1.0h-2.0h.
Optionally, in step 3, the reaction temperature is 50-65 ℃, the reaction time is 2-4 h, and the pH value at the end point of the reaction is 7.0+/-0.2.
Optionally, in step 4, the reaction liquid-solid ratio is (4-6) mL:1g, the reaction time is 2-4 h, the reaction temperature is 65+/-2 ℃, and the pH value of the reaction end point is 10.0-10.5.
Optionally, in step 4, the carbonate solution is (45.+ -.5) g/L Na 2 CO 3 And (15+ -5) g/L NaHCO 3 Is a mixed solution of (a) and (b).
Optionally, in step 5, the reaction time is 2.0h-4.0h, the reaction temperature is 50-80 ℃, and the reaction end point pH value is 12.5-13.5.
Optionally, in step 1, the mass fraction of uranium of the disqualified diuranate is 30% -45% and the mass fraction of iron is 5% -15%.
Optionally, in step 2, the mass fraction of uranium in the filter residue is 5% -8%.
The beneficial effects are that:
(1) And dissolving the disqualified products of the transuranate by adopting hydrochloric acid to dissolve iron impurities in the disqualified products of the transuranate, and removing iron from acidolysis solution by adopting a goethite method to remove the iron in the solution in a precipitation mode.
(2) Through seed crystal induction and long-time aging treatment, iron is removed more thoroughly, and solid-liquid separation is facilitated.
(3) And carbonate is used as a leaching agent, and uranium is leached and extracted from the iron-removing slag and recovered, so that the recovery rate of the uranium is improved.
(4) And (3) respectively recovering uranium from the uranium purified liquid and the uranium alkaline leaching liquid by adopting sodium hydroxide in a uranium precipitation mode to obtain qualified diuranate products.
(5) The invention shortens the treatment process, so that the treatment process flow is simple, flexible and easy to operate, can be used for large-scale production, and can effectively reduce energy consumption and reagent consumption, thereby reducing cost investment.
Drawings
Fig. 1 is a process flow diagram of one embodiment of a method of preparing a diuranate salt by fractional precipitation in accordance with the present invention.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Referring to fig. 1, a process for preparing a uranate salt according to an embodiment of the present invention by fractional precipitation, the detailed process steps are as follows,
and step 1, dissolving unqualified diuranate by hydrochloric acid, and then filtering to obtain an acid solution.
Specifically, the unqualified diuranate sample is obtained from hydrometallurgy of co-associated uranium resources, wherein the diuranate is included, the mass fraction of uranium U is 30% -45%, and the mass fraction of iron Fe is 5% -15%. The acidolysis agent adopted in the embodiment is dilute hydrochloric acid, and the concentration is controlled to be 1-2 mol/L, so that part of soluble components in the unqualified transuranate are dissolved under the action of hydrochloric acid; wherein, the diuranate can be dissolved under the acidic condition, and the impurity iron can also generate ferrous iron under the action of hydrochloric acid, and acid solution after acidolysis and deposition on the filter residue part which is not easy to acidolysis can be obtained after filtering, the filter residue part can be abandoned as waste residue, and the acid solution can be continued to the subsequent extraction operation. Meanwhile, the liquid-solid ratio of the acid dissolution reaction needs to be controlled, namely, the mass of the added unqualified diuranate and the total volume of the solution in the reactor are controlled, and the liquid-solid ratio is controlled to be (1.5-2.0) mL:1g; preferably, the acidolysis reaction time is controlled to be 1 to 1.5 hours; more preferably, the residual H in the solution is also controlled + The concentration is in the range of 0.25mol/L to 0.50mol/L.
And 2, heating the acid solution, adding a preset amount of neutralizing precipitant and hydrogen peroxide, and controlling the reaction temperature and the pH value.
Specifically, the added neutralizing precipitant is sodium hydroxide solution, the mass fraction of sodium hydroxide is more than or equal to 30%, the mass fraction of added hydrogen peroxide is less than 3% and more than 0, the heating temperature is controlled to be 85-90 ℃, the pH value of the reaction end point is 3.2-3.5, the reaction environment of the step is high heat and low acidity environment, the iron removal mode by adopting a goethite method is realized, namely iron in acidolysis solution is removed under acidic condition, the principle is that ferrous iron is firstly converted into ferric iron under the action of hydrogen peroxide, then the ferric iron can generate beta-FeOOH under high heat and low acidity environment, thus goethite-like crystals are formed, and ferric iron precipitation is realized, so that iron in solution is removed. In addition, in order to further reduce the concentration of iron ions in the solution after iron removal, all the products after goethite reaction can be transferred into an aging tank, and the iron removal effect can be improved by aging for 1.0-2.0 h based on the precipitation generated in the reaction.
Preferably, 5% -10% of seed crystals can be reserved in the tank, then aging reaction is carried out for 1.0h-2.0h, treatment by adopting a seed crystal induction and aging mode is realized, the concentration of iron ions in the solution after iron removal is reduced to 0.08mg/L, the iron removal effect is further improved, and finally filtration treatment is carried out to obtain uranium purified solution and iron removal slag. Generally, the mass fraction of uranium in the de-ironing slag is 5% -8%, and uranium extraction treatment can be further carried out.
And step 3, adding a preset amount of sodium hydroxide solution into the uranium purified solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate. Specifically, a sodium hydroxide solution with mass fraction more than or equal to 30% is added into the uranium purification liquid, so that the uranium purification liquid and sodium hydroxide are neutralized and precipitated to further realize the purpose of recycling uranium, and the neutralization and precipitation reaction time is controlled to be 2.0-4.0 h, the temperature is 50-65 ℃, and the end point pH value is 7.0+/-0.2 in the reaction. And then aging, filtering and washing a filter cake to obtain a qualified sodium diuranate product.
And 4, adding a preset amount of carbonate solution into the iron-removing slag, controlling the reaction liquid-solid ratio, the reaction temperature and the pH value, and then filtering to obtain uranium alkaline leaching solution.
Specifically, adding carbonate into the iron-removing slag to extract uranium by alkaline leaching, wherein the carbonate solution is Na (45+/-5) g/L 2 CO 3 And (15+ -5) g/L NaHCO 3 Controlling the liquid-solid ratio of the reaction to be (4-6) mL:1g, wherein the reaction time is 2-4 h, the reaction temperature is 65+/-2 ℃, the pH value of the reaction end point is 10.0-10.5, and the obtained solution is uranium alkaline leaching solution which is sodium uranyl tricarbonate solution after filtration; the filter cake is pulped and washed to obtain leaching slag, and the mass fraction of uranium in the slag is 0.5% -1.5%. The step realizes the extraction of uranium from the iron-removing slag by leaching, and further improves the recovery rate of uranium.
And 5, adding a preset amount of sodium hydroxide solution into the uranium alkaline leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
Specifically, naOH solution with concentration higher than or equal to 30% is added into uranium alkaline leaching solution to precipitate uranium, wherein the precipitation reaction time is controlled to be 2.0-4.0 h, the temperature is 50-80 ℃, the end point pH value is 12.5-13.5, and then the qualified sodium diuranate product is prepared through ageing, filtering and filter cake washing. The homogeneous amount of the sodium diuranate meets the requirements of technical condition of diuranate (EJ/T803-93).
In the embodiment, the unqualified diuranate is acidolyzed, the goethite method is adopted to completely precipitate iron at high temperature and lower pH value, and the obtained uranium purified solution and iron removal slag are respectively recycled to uranium; and selecting carbonate as a leaching agent, leaching, extracting and recovering uranium from the iron-removing slag to obtain uranium alkaline leaching liquid, and recovering uranium from the uranium purified liquid and the uranium alkaline leaching liquid in a uranium precipitation mode by adopting sodium hydroxide respectively to prepare qualified diuranate products, wherein the standard quality requirement is met. In addition, the whole treatment process flow is simple and flexible, easy to operate and easy for large-scale production, and can effectively reduce energy consumption and reagent consumption, further reduce cost input and realize effective recycling of the uranate.
Further, in order to better illustrate the specific process of the present invention, the following operations are performed by randomly taking samples of different batches of transuranate rejects, and performing the following operations in multiple groups, and the method of the present invention is further described below with reference to specific examples.
Example 1
And 1, dissolving hydrochloric acid.
500g of the disqualified diuranate sample (U: 39.37% and Fe: 7.07%) is weighed into a 2000mL glass beaker, 750mL of industrial water is added, stirring is started, 110mL of 31.12% HCl solution by mass fraction is added, the acid dissolution reaction time is controlled to be 1.5h, acid dissolution liquid is obtained by filtration, filter residues are obtained by washing 2 times of 0.5BV volume washing water, and the filter residues are discarded.
And 2, deironing the acid solution.
The acid solution was placed in a 2000mL glass beaker, stirring was turned on andheating, and adding 31% NaOH solution and 3%H 2 O 2 The reaction temperature of the solution for removing iron by a goethite method is controlled to be 87+/-2 ℃, the end point pH value is controlled to be 3.5, and the time is controlled to be 2.0h. Transferring all the iron-removing feed liquid into an ageing tank, wherein 8% of seed crystals are reserved in the tank, and ageing time is 1.5h; obtaining uranium purified liquid through hot filtration (the material temperature is more than or equal to 55 ℃), wherein a filter cake is iron-removing slag, and the mass fraction of uranium in the iron-removing slag is U:7.42%.
And 3, precipitating uranium purified liquid to prepare sodium diuranate.
And adding a NaOH solution with the mass fraction of 31% into the uranium purified solution to precipitate uranium, controlling the neutralization precipitation reaction temperature to be 62+/-2 ℃, controlling the end point pH value to be 7.0 and controlling the time to be 3.0 hours, and aging, filtering and washing a filter cake to obtain a qualified sodium diuranate product.
And 4, leaching the iron-removing slag by an alkaline method.
Placing the iron-removed slag into a 1000mL glass beaker, starting stirring and heating, and adding 47g/L Na into the beaker 2 CO 3 NaHCO 12g/L 3 Mixing the solution, and controlling the liquid-solid ratio of the alkaline leaching reaction to be 4mL:1g, a reaction time of 3.5h, a reaction temperature of 65+ -2deg.C and a reaction end pH value of 10.2. Filtering to obtain a filter clear liquid which is uranium alkaline leaching liquid, pulping and washing a filter cake to obtain leaching residues, wherein the filter cake is alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:0.98%.
And 5, precipitating uranium alkaline leaching solution to prepare sodium diuranate.
Adding a NaOH solution with the mass fraction of 31% into uranium alkaline leaching solution, controlling the precipitation reaction temperature to 75+/-2 ℃, the reaction end point pH value to 13.2 and the reaction time to 3.0h, and then aging, filtering and washing a filter cake to prepare a qualified sodium diuranate product.
Further, uniformly mixing the sodium diuranate products prepared by the two fractional precipitation steps, sampling and analyzing the sodium diuranate products (based on dry basis): u:51.12% SO 4 2- ：0.14％、PO 4 3- ：0.15％、SiO 2 :0.35%, F-:0.19%, cl-:0.26%, fe:0.37 percent, and the product quality meets the technical condition of transuranateThe requirements of the above-mentioned patent.
Example 2
And 1, dissolving hydrochloric acid.
500g of the disqualified diuranate sample (U: 39.37% and Fe: 7.07%) is weighed into a 2000mL glass beaker, 750mL of industrial water is added, stirring is started, 110mL of HCl solution with mass fraction of 30.54% is added, the acid dissolution reaction time is controlled to be 1.0h, acid dissolution liquid is obtained through filtration, filter residues are obtained after 2 times of washing with water with volume of 0.5BV, and the filter residues are discarded.
And 2, deironing the acid solution.
The acid solution was placed in a 2000mL glass beaker, stirred and warmed, and 31% NaOH solution and 2% H by mass were added 2 O 2 The reaction temperature of the solution for removing iron by a goethite method is controlled to be 87+/-2 ℃, the end point pH value is controlled to be 3.3, and the time is controlled to be 1.0h. Transferring all the iron-removing feed liquid into an ageing tank, reserving 5% of seed crystals in the tank, and ageing for 1.5h; obtaining uranium purified liquid through hot filtration (the material temperature is more than or equal to 55 ℃), wherein a filter cake is iron-removing slag, and the mass fraction of uranium in the iron-removing slag is U:5.26%.
And 3, precipitating uranium purified liquid to prepare sodium diuranate.
And adding a NaOH solution with the mass fraction of 31% into the uranium purified solution to precipitate uranium, controlling the neutralization precipitation reaction temperature to be 60+/-2 ℃, controlling the end point pH value to be 7.1 and the time to be 2.5 hours, and aging, filtering and washing a filter cake to obtain a qualified sodium diuranate product.
And 4, leaching the iron-removing slag by an alkaline method.
Placing the iron-removed slag into a 1000mL glass beaker, starting stirring and heating, and adding 47g/L Na into the beaker 2 CO 3 NaHCO 12g/L 3 Mixing the solution, and controlling the liquid-solid ratio of the alkaline leaching reaction to be 5mL:1g, a reaction time of 3.0h, a reaction temperature of 65+ -2deg.C and a reaction end pH of 10.4. Filtering to obtain a filter clear liquid which is uranium alkaline leaching liquid, pulping and washing a filter cake to obtain leaching residues, wherein the filter cake is alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:0.84%.
And 5, precipitating uranium alkaline leaching solution to prepare sodium diuranate.
Adding a 31% NaOH solution into uranium alkaline leaching solution, controlling the precipitation reaction temperature to 75+/-2 ℃, the reaction end point pH value to 13.0 and the reaction time to 2.0 hours, and then aging, filtering and washing a filter cake to prepare a qualified sodium diuranate product.
Further, uniformly mixing the sodium diuranate products prepared by the two fractional precipitation steps, sampling and analyzing the sodium diuranate products (based on dry basis): u:54.81% SO 4 2- ：0.10％、PO 4 3- ：0.18％、SiO 2 :0.21%, F-:0.15%, cl-:0.14%, fe:0.18 percent, and the product quality meets the requirements of diuranate technical conditions.
Example 3
And 1, dissolving hydrochloric acid.
500g of the disqualified diuranate sample (U: 39.37% and Fe: 7.07%) is weighed into a 2000mL glass beaker, 750mL of industrial water is added, stirring is started, 110mL of 32.01% HCl solution by mass fraction is added, the acid dissolution reaction time is controlled to be 1.0h, acid dissolution liquid is obtained through filtration, filter residues are obtained after 2 times of washing with 0.5BV volume of washing water, and the filter residues are discarded.
And 2, deironing the acid solution.
The acid solution was placed in a 2000mL glass beaker, stirred and warmed, and 31% NaOH solution and 2.5% H by mass were added 2 O 2 Controlling the reaction temperature of the solution at 87+/-2 ℃ and the final pH value at 3.4 for 4.0 hours, and removing iron by a goethite method. Transferring all the iron-removing feed liquid into an ageing tank, wherein 10% of seed crystals are reserved in the tank, and the ageing time is 1.5h; obtaining uranium purified liquid through hot filtration (the material temperature is more than or equal to 55 ℃), wherein a filter cake is iron-removing slag, and the mass fraction of uranium in the iron-removing slag is U:6.62%.
And 3, precipitating uranium purified liquid to prepare sodium diuranate.
And adding a NaOH solution with the mass fraction of 31% into the uranium purified solution to precipitate uranium, controlling the neutralization precipitation reaction temperature to 55+/-2 ℃, controlling the end point pH value to 6.9 and the time to 2.5 hours, and aging, filtering and washing a filter cake to obtain a qualified sodium diuranate product.
And 4, leaching the iron-removing slag by an alkaline method.
Placing the iron-removed slag into a 1000mL glass beaker, starting stirring and heating, and adding 47g/L Na into the beaker 2 CO 3 NaHCO 12g/L 3 Mixing the solution, and controlling the liquid-solid ratio of the alkaline leaching reaction to be 4.5mL:1g, a reaction time of 3.0h, a reaction temperature of 65+ -2deg.C and a reaction end pH of 10.2. Filtering to obtain acid solution which is uranium alkaline leaching solution, pulping and washing a filter cake to obtain leaching residues, wherein the filter cake is alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:0.74%.
And 5, precipitating uranium alkaline leaching solution to prepare sodium diuranate.
Adding a 31% NaOH solution into uranium alkaline leaching solution, controlling the precipitation reaction temperature to 75+/-2 ℃, the reaction end point pH value to 13.0 and the reaction time to 2.5 hours, and then aging, filtering and washing a filter cake to prepare a qualified sodium diuranate product.
Further, uniformly mixing the sodium diuranate products prepared by the two fractional precipitation steps, sampling and analyzing the sodium diuranate products (based on dry basis): u:52.45%, SO 4 2- ：0.10％、PO 4 3- ：0.27％、SiO 2 :0.41%, F-:0.18%, cl-:0.20%, fe:0.29 percent, and the product quality meets the requirements of diuranate technical conditions.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or system that comprises the element.
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.

Claims (10)

1. A process for the preparation of diuranate by fractional precipitation comprising the steps of:
step 1, dissolving unqualified diuranate with hydrochloric acid, and then filtering to obtain an acid solution;
step 2, heating the acid solution, adding a preset amount of neutralizing precipitant and hydrogen peroxide, controlling the reaction temperature and the pH value, and then aging and filtering to obtain uranium purified solution and iron-removing slag; wherein the reaction temperature is 85-90 ℃, and the pH value of the reaction end point is 3.2-3.5;
step 3, adding a preset amount of sodium hydroxide solution into the uranium purified solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate;
step 4, adding a preset amount of carbonate solution into the iron-removing slag, controlling the reaction liquid-solid ratio, the reaction temperature and the pH value, and then filtering to obtain uranium alkaline leaching solution;
and 5, adding a preset amount of sodium hydroxide solution into the uranium alkaline leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
2. The method for producing a diuranate by fractional precipitation according to claim 1, wherein in step 1, the acid dissolution reaction liquid-solid ratio is (1.5 to 2.0) mL:1g, the reaction time is 1H-1.5H, the residual H + The concentration is 0.25mol/L to 0.50mol/L.
3. The method for producing a diuranate by fractional precipitation according to claim 1, wherein in step 2, the neutralizing precipitant is a sodium hydroxide solution having a mass fraction of 30% or more; the mass fraction of the hydrogen peroxide is less than 3%.
4. The method for preparing a diuranate by fractional precipitation according to claim 1 wherein in step 2 the aging time is 1.0h to 2.0h.
5. The method for preparing a diuranate by fractional precipitation according to claim 1, wherein in step 3, the reaction temperature is 50 ℃ to 65 ℃, the reaction time is 2 hours to 4 hours, and the reaction end point pH value is 7.0±0.2.
6. The method for producing a diuranate by fractional precipitation according to claim 1, wherein in step 4, the reaction liquid-solid ratio is (4 to 6) mL:1g, the reaction time is 2-4 h, the reaction temperature is 65+/-2 ℃, and the pH value of the reaction end point is 10.0-10.5.
7. The method for producing a diuranate by fractional precipitation according to claim 1, wherein in step 4, the carbonate solution is (45.+ -.5) g/L Na 2 CO 3 And (15+ -5) g/L NaHCO 3 Is a mixed solution of (a) and (b).
8. The method for preparing a diuranate by fractional precipitation according to claim 1, wherein in step 5, the reaction time is 2.0 to 4.0 hours, the reaction temperature is 50 to 80 ℃ and the reaction end point pH is 12.5 to 13.5.
9. The method for producing a diuranate by fractional precipitation according to any of claims 1 to 8, characterized in that in step 1 the mass fraction of uranium of the reject diuranate is 30% to 45% and the mass fraction of iron is 5% to 15%.
10. The method for preparing a diuranate by fractional precipitation according to any of claims 1 to 8, characterized in that in step 2 the mass fraction of uranium in the filter residue is 5% to 8%.
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CA685437A (en) * 1964-04-28 Rio Algom Mines Limited Purification of uranium yellow cake
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BR7602512A (en) * 1975-04-24 1976-10-19 Fmc Corp PROCESS FOR RECOVERY OF URANIUM CONTENT AS URANYL PEROXIDE
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