CN117587276A - Method for preparing diuranate by alkaline leaching - Google Patents
Method for preparing diuranate by alkaline leaching Download PDFInfo
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- CN117587276A CN117587276A CN202311506696.0A CN202311506696A CN117587276A CN 117587276 A CN117587276 A CN 117587276A CN 202311506696 A CN202311506696 A CN 202311506696A CN 117587276 A CN117587276 A CN 117587276A
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- diuranate
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- alkaline leaching
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- 238000002386 leaching Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 84
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 230000035484 reaction time Effects 0.000 claims description 20
- 238000004090 dissolution Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 229910052598 goethite Inorganic materials 0.000 description 7
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 206010015548 Euthanasia Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KGUNSXBRJUFYRR-UHFFFAOYSA-N sodium uranium Chemical compound [Na][U] KGUNSXBRJUFYRR-UHFFFAOYSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 229910003153 β-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
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- Mechanical Engineering (AREA)
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Abstract
The invention discloses a method for preparing diuranate by alkaline leaching, which comprises the following steps: step 1, dissolving unqualified diuranate by carbonate, and then filtering to obtain uranium alkali leaching solution and alkali leaching slag; step 2, dissolving alkaline leaching residues with dilute hydrochloric acid, and then filtering to obtain an acid solution; step 3, 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; wherein the reaction temperature is 85-90 ℃, and the pH value of the reaction end point is 3.2-3.5; and 4, adding a preset amount of sodium hydroxide solution into the uranium purified solution and the uranium alkali leaching solution to precipitate uranium, 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
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for preparing diuranate by alkaline leaching.
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 co-associated uranium resources is achieved, and the method has good industrial value. The invention patent with the prior patent publication number of CN111945001A discloses a method for treating monazite euthanasia slag, which discloses that the separation of iron and uranium adopts an extraction mode; however, the separation of uranium from other metals is not useful 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 alkaline leaching, which aims to solve the technical problem that the existing uranate defective products cannot be used for efficiently recovering uranium.
To achieve the above object, the present invention provides a method for preparing diuranate by alkaline leaching, comprising the steps of:
step 1, dissolving unqualified diuranate by carbonate, and then filtering to obtain uranium alkali leaching solution and alkali leaching slag;
step 2, dissolving alkaline leaching residues with dilute hydrochloric acid, and then filtering to obtain an acid solution;
step 3, 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; wherein the reaction temperature is 85-90 ℃, and the pH value of the reaction end point is 3.2-3.5;
and 4, adding a preset amount of sodium hydroxide solution into the uranium purified solution and the uranium alkali leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
Optionally, in step 1, the carbonate dissolution 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 1, 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 2, the liquid-solid ratio of the hydrochloric acid dissolution reaction 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, hydrochloric acid is added to a solubility of 1-2mol/L.
Optionally, in step 3, 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 3, the aging time is 1.0h-2.0h.
Optionally, in step 4, the sodium hydroxide solution solubility is greater than or equal to 30% by mass.
Optionally, in the step 4, the reaction time is 2.0-4.0 h, 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%.
The beneficial effects are that:
(1) The method comprises the steps of adopting carbonate to dissolve disqualified products of uranate to obtain uranium alkaline leaching solution and alkaline leaching slag, adopting hydrochloric acid to dissolve alkaline leaching slag to realize iron impurity dissolution in the alkaline leaching slag, and adopting goethite method to remove iron in the uranium alkaline leaching solution, namely removing iron in the uranium alkaline leaching solution in a precipitation mode, and further carrying out seed crystal induction and long-time aging treatment to remove iron more thoroughly and be beneficial to solid-liquid separation.
(2) And recycling uranium from the uranium purified liquid and the mixed liquid of the uranium alkaline leaching liquid by adopting sodium hydroxide in a uranium precipitation mode to obtain a qualified diuranate product.
(3) 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 the present invention for preparing transuranate by alkaline leaching.
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 diuranate salt by alkaline leaching according to an embodiment of the present invention, the detailed process steps are as follows,
and step 1, dissolving unqualified diuranate by using carbonate, and then filtering to obtain uranium alkali leaching liquid and alkali leaching slag.
In this embodiment, the unqualified diuranate sample is obtained from hydrometallurgy of co-associated uranium resources, wherein the diuranate sample includes diuranate and other impurities, and the mass fraction of uranium U is 30% -45% and the mass fraction of iron Fe is 5% -15%. Wherein the carbonate solution is (45+ -5) g/L Na 2 CO 3 And (15+ -5) g/L NaHCO 3 Adding carbonate into the disqualified products of the transuranate to extract uranium by an alkaline method, and controlling the liquid-solid ratio of the alkaline leaching reaction to be (4-6) mL, wherein 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; at the same timeThe uranium alkaline leaching liquid and alkaline leaching slag are obtained through filtration, the uranium alkaline leaching liquid is mainly sodium uranyl tricarbonate solution, the mass fraction of uranium in the alkaline leaching slag is 2.0% -6.5%, and then the purpose of leaching and extracting uranium from unqualified diuranate samples under the action of carbonate is achieved.
And 2, dissolving the alkaline leaching residues with dilute hydrochloric acid, and then filtering to obtain an acid solution.
Specifically, the hydrochloric acid solution is diluted hydrochloric acid, the concentration is controlled to be 1-2mol/L, and the purpose is to dissolve part of soluble components of the alkaline leaching residue 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 which is not easy to acidolysis can be obtained after filtering, the 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 alkaline leaching residue 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 acid content in the solution is controlled to be in the range of 0.25mol/L to 0.50mol/L.
And step 3, 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.
Specifically, the added neutralizing precipitant is sodium hydroxide solution, the mass fraction of the sodium hydroxide is equal to or equal to 30%, the mass fraction of the added hydrogen peroxide is smaller than or equal to 3% and is larger than 0%, the heating temperature is controlled to be 85-90 ℃, the pH value of the reaction end point is controlled to be 3.2-3.5, and the reaction environment of the step is a high-heat and low-acidity environment, so that the aim of removing iron by adopting a goethite method is fulfilled, namely iron in acidolysis solution is removed under an 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 the high-heat and low-acid environment, namely goethite-like crystals are formed, and ferric iron precipitation is realized. 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 treated deironing slag is 0.5-1.5%, and the deironing slag is temporarily treated; the solution after iron removal is filtered to obtain uranium purified solution, and the uranium purified solution can be continuously processed for standby.
And 4, adding a preset amount of sodium hydroxide solution into the uranium purified solution and the uranium alkali leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
Specifically, adding NaOH solution with concentration higher than or equal to 30% into uranium purified solution and uranium alkaline leaching solution mixed solution to precipitate uranium, wherein the precipitation reaction time is controlled to be 2.0-4.0 h, the temperature is controlled to be 50-80 ℃, the end point pH value is controlled to be 12.5-13.5, and then aging, filtering and filter cake washing are carried out to prepare qualified sodium diuranate products. The homogeneous amount of the sodium diuranate meets the requirements of technical condition of diuranate (EJ/T803-93).
In the embodiment, unqualified diuranate is dissolved through carbonate to obtain uranium alkaline leaching solution and alkaline leaching residue, the alkaline leaching residue is continuously dissolved under the action of acidity to obtain acidolysis solution, and then iron in the acidolysis solution is completely precipitated by adopting a goethite method at high temperature and lower pH value to obtain uranium purified solution; and finally, mixing the uranium purified solution and uranium alkaline leaching solution, and recovering uranium by adopting a mode of precipitating uranium by sodium hydroxide to prepare qualified diuranate products, wherein the standard quality requirements are 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 step 1, dissolving and leaching carbonate.
100g of transuranate reject (U: 39.37%, fe: 7.07%) was placed in a 1000mL glass beaker, and 500mL of 45g/LNa was added 2 CO 3 、12g/LNaHCO 3 The mixed solution is stirred and heated, the reaction time of alkaline leaching is controlled to be 3.5 hours, the reaction temperature is 65+/-2 ℃, and the pH value of the reaction end point is controlled to be 10.2. And filtering to obtain a filtered clear liquid, wherein the filtered clear liquid is mainly uranium alkaline leaching liquid, a filter cake is subjected to pulping and washing to obtain leaching residues, the leaching residues are alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:4.51%.
And 2, acid dissolving alkali leaching slag.
Weighing the alkaline leaching residue, placing the alkaline leaching residue in a 500mL glass beaker, adding a proper amount of water, starting stirring, adding an HCl solution with the mass fraction of 31.12%, controlling the acid dissolution reaction liquid-solid ratio to be 2 mL/1 g and the reaction time to be 1.5h, filtering to obtain a filtered clear liquid and filter residues, taking the filtered clear liquid as acidolysis solution for standby, and washing the filter residues with washing water with the volume of 0.5BV for 2 times to obtain the waste treatment of the dissolved residue.
And 3, iron removal treatment.
Placing acidolysis solution in a 500mL glass beaker, starting stirring and heating, and adding 31% NaOH solution and 2.9% H 2 O 2 The reaction temperature for removing iron is controlled to be 87+/-2 ℃, the pH value of the reaction end point is 3.5, and the reaction time is 2.0h, so that iron is removed by a goethite method. Transferring the iron-removing feed liquid to an aging tank, wherein 10% of seed crystals are reserved in the tank, and the aging 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:0.82 percent of iron-removing slag temporary storage treatment.
And 4, preparing qualified sodium diuranate.
And mixing the uranium purified solution and the uranium alkaline leaching solution, adding a 31% NaOH solution by mass fraction for precipitation and recycling uranium, controlling the precipitation reaction time to be 3.0h, the reaction temperature to be 75+/-2 ℃ and the reaction end point pH value to be 13.0, and carrying out precipitation aging, filtering and filter cake washing to obtain the sodium diuranate product. Sampling and analyzing, namely, sodium diuranate product (based on dry basis): u:52.87%, SO 4 2- ：0.64％、PO 4 3- ：0.15％、SiO 2 ：0.15％、F - ：0.10％、Cl - :0.16%, fe:0.39 percent, and the product quality meets the requirements of diuranate technical conditions.
Example 2
And step 1, dissolving and leaching carbonate.
100g of transuranate reject (U: 39.37%, fe: 7.07%) was placed in a 1000mL glass beaker, and 500mL of 48g/LNa was added 2 CO 3 、15g/LNaHCO 3 The mixed solution is stirred and heated, the reaction time of alkaline leaching is controlled to be 3.0h, the reaction temperature is 65+/-2 ℃, and the pH value of the reaction end point is controlled to be 10.4. And filtering to obtain a filtered clear liquid, wherein the filtered clear liquid is mainly uranium alkaline leaching liquid, a filter cake is subjected to pulping and washing to obtain leaching residues, the leaching residues are alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:6.03%.
And 2, acid dissolving alkali leaching slag.
Weighing the alkaline leaching residue, placing the alkaline leaching residue in a 500mL glass beaker, adding a proper amount of water, starting stirring, adding an HCl solution with the mass fraction of 32.42%, controlling the liquid-solid ratio of an acid dissolution reaction to be 1.6 mL/1 g and the reaction time to be 1.5h, filtering to obtain a filtered clear liquid and filter residues, taking the filtered clear liquid as acidolysis solution for standby, and washing the filter residues with washing water with the volume of 0.5BV for 2 times to obtain the waste treatment of the dissolved residue.
And 3, iron removal treatment.
Placing acidolysis solution in 500mL glass beaker, stirring and heating, adding 31% NaOH solution and 3%H 2 O 2 The reaction temperature for removing iron is controlled to 88+/-2 ℃, the end point pH value is 3.4, and the reaction time is 2.0h, so that iron is removed by a goethite method. And thenTransferring the iron-removing feed liquid to an aging tank, wherein 8% of seed crystals are reserved in the tank, and the aging time is 2.0h; 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:0.61 percent of iron-removing slag temporary storage treatment.
And 4, preparing qualified sodium diuranate.
And (3) mixing the uranium purified solution and the uranium alkaline leaching solution, adding 31% NaOH solution by mass fraction for precipitating and recovering uranium, controlling the precipitation reaction time to be 3.0h, the reaction temperature to be 75+/-2 ℃ and the reaction end point pH value to be 13.5, and obtaining a sodium diuranate product through precipitation aging, filtering and filter cake washing. Sampling and analysis, sodium uranium acid product (based on dry basis): u:53.16%, SO 4 2- ：0.58％、PO 4 3- ：0.12％、SiO 2 ：0.13％、F - ：0.11％、Cl - :0.22%, fe:0.30 percent, and the product quality meets the requirements of diuranate technical conditions.
Example 3
And step 1, dissolving and leaching carbonate.
100g of transuranate reject (U: 39.37%, fe: 7.07%) was placed in a 1000mL glass beaker, and 500mL of 44g/LNa was added 2 CO 3 、17g/LNaHCO 3 The mixed solution is stirred and heated, the reaction time of alkaline leaching is controlled to be 3.0h, the reaction temperature is 65+/-2 ℃, and the pH value of the reaction end point is controlled to be 10.1. And filtering to obtain a filtered clear liquid, wherein the filtered clear liquid is mainly uranium alkaline leaching liquid, a filter cake is subjected to pulping and washing to obtain leaching residues, the leaching residues are alkaline leaching residues, and the mass fraction of uranium in the alkaline leaching residues is U:3.95%.
And 2, acid dissolving alkali leaching slag.
Weighing the alkaline leaching residue, placing the alkaline leaching residue in a 500mL glass beaker, adding a proper amount of water, starting stirring, adding an HCl solution with the mass fraction of 31.78%, controlling the liquid-solid ratio of an acid dissolution reaction to be 1.5 mL/1 g and the reaction time to be 1h, filtering to obtain a filtered clear liquid and filter residues, taking the filtered clear liquid as acidolysis solution for standby, and washing the filter residues with washing water with the volume of 0.5BV for 2 times to obtain the waste treatment of the dissolved residue.
And 3, iron removal treatment.
The acidolysis solution is placed in a 500mL glass beaker, stirring and heating are started, 31 percent NaOH solution with the mass fraction of 2.8 percent H is added 2 O 2 The reaction temperature for removing iron is controlled to be 87+/-2 ℃, the end point pH value is 3.3, and the time is 2.0h, so that iron is removed by a goethite method. Transferring the iron-removing feed liquid to an aging tank, wherein 8% of seed crystals are reserved in the tank, and the aging time is 2.0h; 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:0.58 percent of iron-removing slag temporary storage treatment.
And 4, preparing qualified sodium diuranate.
And mixing the uranium purified solution and the uranium alkaline leaching solution, adding a 31% NaOH solution by mass fraction for precipitation to recover uranium, controlling the precipitation reaction time to be 4.0h, the reaction temperature to be 75+/-2 ℃ and the reaction end point pH value to be 12.5, and carrying out precipitation aging, filtering and filter cake washing to obtain the sodium diuranate product. Sampling and analyzing, namely, sodium diuranate product (based on dry basis): u:53.84%, SO 4 2- ：0.60％、PO 4 3- ：0.13％、SiO 2 ：0.12％、F - ：0.15％、Cl - :0.15%, fe:0.28 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 method for preparing diuranate by alkaline leaching, which is characterized by comprising the following steps:
step 1, dissolving unqualified diuranate by carbonate, and then filtering to obtain uranium alkali leaching solution and alkali leaching slag;
step 2, dissolving alkaline leaching residues with dilute hydrochloric acid, and then filtering to obtain an acid solution;
step 3, 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; wherein the reaction temperature is 85-90 ℃, and the pH value of the reaction end point is 3.2-3.5;
and 4, adding a preset amount of sodium hydroxide solution into the uranium purified solution and the uranium alkali leaching solution to precipitate uranium, and then aging and filtering to obtain qualified sodium diuranate.
2. The method for producing a diuranate by alkaline leaching according to claim 1, wherein in step 1, the carbonate dissolution 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.
3. The method for producing a diuranate by alkaline leaching as claimed in claim 2, wherein in step 1, 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).
4. The method for producing a diuranate by alkaline leaching according to claim 1, wherein in step 2, a liquid-solid ratio of a hydrochloric acid dissolution reaction is (1.5 to 2.0) mL:1g.
5. The method for preparing diuranate by alkaline leaching according to claim 4, wherein in the step 2, the hydrochloric acid dissolution reaction time is 1H to 1.5H, and the reaction end point is the remaining H + The concentration is 0.25mol/L to 0.50mol/L.
6. The method for preparing diuranate by alkaline leaching according to claim 1, wherein in the step 3, the neutralization 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%.
7. The method for producing transuranate by alkaline leaching as claimed in claim 6, wherein in step 3, the aging time is 1.0h to 2.0h.
8. The method for producing diuranate by alkaline leaching according to claim 1, wherein in step 4, the sodium hydroxide solution solubility is 30% by mass or more.
9. The method for preparing diuranate by alkaline leaching according to claim 8, wherein in the step 4, the reaction time is 2.0 to 4.0 hours, the reaction temperature is 50 to 80 ℃, and the reaction end point pH value is 12.5 to 13.5.
10. The method for preparing diuranate by alkaline leaching according to any one of claims 1 to 9, wherein 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%.
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