CN115216655B - Extraction method for uranium in alkaline residue formed by precipitation of uranium-containing wastewater - Google Patents
Extraction method for uranium in alkaline residue formed by precipitation of uranium-containing wastewater Download PDFInfo
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- CN115216655B CN115216655B CN202210716859.7A CN202210716859A CN115216655B CN 115216655 B CN115216655 B CN 115216655B CN 202210716859 A CN202210716859 A CN 202210716859A CN 115216655 B CN115216655 B CN 115216655B
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 112
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000605 extraction Methods 0.000 title claims abstract description 63
- 239000002351 wastewater Substances 0.000 title claims abstract description 37
- 238000001556 precipitation Methods 0.000 title claims abstract description 20
- 239000012530 fluid Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 34
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002901 radioactive waste Substances 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 description 10
- 239000003518 caustics Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 240000000950 Hippophae rhamnoides Species 0.000 description 1
- 235000003145 Hippophae rhamnoides Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002925 low-level radioactive waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000442 triuranium octoxide Inorganic materials 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
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- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of radioactive waste treatment and recovery, and relates to a method for extracting uranium from uranium-containing wastewater by precipitation to form alkaline residue. The extraction method comprises the following steps: (1) pretreatment of uranium-containing alkaline residue: precipitating the uranium-containing wastewater to form alkaline residue for steam oxidation reaction; (2) Supercritical CO 2 Fluid extraction: in supercritical CO 2 In fluid extraction equipment, the uranium-containing wastewater after the water vapor oxidation reaction is precipitated to form alkaline residue, and the alkaline residue is mixed with saturated aluminum nitrate solution and then is introduced into a reactor containing TBP-HNO 3 Supercritical CO of (C) 2 Supercritical CO of fluids 2 Extracting fluid; (3) separating and collecting uranium-containing solution: supercritical CO 2 Supercritical CO after fluid extraction 2 Carrying uranium into a separation device in which the pressure is reduced, CO 2 Gasifying and collecting uranium-containing solution in the separation equipment. By utilizing the extraction method of uranium in the alkaline residue formed by the uranium-containing wastewater precipitation, the uranium can be extracted from the alkaline residue formed by the uranium-containing wastewater precipitation with high extraction rate and low secondary waste production.
Description
Technical Field
The invention belongs to the technical field of radioactive waste treatment and recovery, and relates to a method for extracting uranium from uranium-containing wastewater by precipitation to form alkaline residue.
Background
And (3) forming wet alkaline residues after ammonium salt precipitation of uranium-containing wastewater generated in the uranium element production process, and temporarily storing the wet alkaline residues in the form of dry alkaline residues after calcining at a high temperature of about 800 ℃ to reduce the volume and the weight. At present, the dry caustic sludge stored in only 812 factories in China is up to 60 tons, which not only causes the waste of uranium resources, but also has the risk of nuclear material diffusion. The alkaline residue has high uranium content and high U-235 abundance, and has high recovery value. However, the alkali slag has complex composition and various impurity elements have unfixed composition, so that no mature process and equipment for recycling uranium from the alkali slag exist at present.
The company Alfa and university of Edahu have cooperated to develop a technique for recovering uranium from the ashes of incinerators in the plant Richland uranium fuel. The method for treating alkaline residue in Richland factory includes such steps as pretreating by solvent extraction, processing in ADU line by ADU flow, extracting various waste residues by solvent extraction, extracting uranium into solution by acid leaching or other means, and extracting to obtain uranium for primary purification. The uranium recovery technology in the caustic sludge from the Richland plant is not technically transferred and therefore its core process technology is not known.
In the 70 s of the 20 th century, nuclear fuel production companies in middle nuclear construction research on the recycling process of uranium in uranium-containing alkaline residues, establish the treatment processes of ball milling, nitric acid leaching, hydrogen peroxide precipitation and oxidation calcination, but have lower leaching rate of uranium, and cannot reach the wastewater discharge standard after the leaching solution is treated. Zhao Ning the above process route is improved to prepare nuclear pure UO 2 (NO 3 ) 2 The solution still has the problems of long process flow, difficult operation and the like. Xu Na and the like research the dissolution and leaching of uranium in natural high-grade uranium waste residues, and adopt treatment processes such as cyclic dissolution, nitric acid leaching, curing by concentrated acid, high-temperature roasting and the like, and the result shows that the content of the final uranium in the residues can be reduced to 0.105%, and the total dissolution and leaching rate of the uranium reaches 99.82%, but the adopted reagent has high corrosiveness and severe conditions, and industrial application is difficult to realize, so that an extraction device of uranium in uranium-containing wastewater sedimentary residues is not established.
In summary, the extraction of uranium in uranium-containing alkaline residues is currently in laboratory research stage, mainly nitric acid leaching and solvent extraction, and other means for enhancing leaching are adopted. In the experimental process, a large amount of acid reagent is required to be consumed, a large amount of secondary waste liquid is generated, the experimental result is unsatisfactory, and the experimental result has no industrial application value.
Supercritical CO 2 The fluid extraction technology is a novel separation technology developed in the 90 th century. The technique utilizes supercritical CO 2 Strong fluidThe penetrability and the strong solubility can realize the extraction of a small amount of target substances in a large-volume solid matrix. Currently, supercritical CO 2 The fluid extraction technology has realized industrial production in the extraction of organic substances such as sea buckthorn oil, essence, essential oil and the like, and is mostly in the laboratory research stage in the extraction of metal ions.
Supercritical CO 2 And the research objects are mainly uranyl solution, triuranium octoxide, uranium dioxide and other simple systems or simulation samples. She Shuang and the like using supercritical CO 2 The extraction rate of uranium in untreated caustic sludge can reach 90% by fluid static extraction, but the extraction rate still cannot meet the requirements of industrial use.
Disclosure of Invention
The invention aims to provide an extraction method of uranium in uranium-containing wastewater precipitation forming alkaline residue, so that uranium can be extracted from the uranium-containing wastewater precipitation forming alkaline residue with high extraction rate and low secondary waste production.
To achieve the object, in a basic embodiment, the present invention provides a method for extracting uranium from uranium-containing wastewater precipitated to form alkaline residue, the method comprising the steps of:
(1) Pretreatment of uranium-containing alkaline residue: precipitating the uranium-containing wastewater to form alkaline residue for steam oxidation reaction;
(2) Supercritical CO 2 Fluid extraction: in supercritical CO 2 In fluid extraction equipment, the uranium-containing wastewater after the water vapor oxidation reaction is precipitated to form alkaline residue, and the alkaline residue is mixed with saturated aluminum nitrate solution and then is introduced into a reactor containing TBP-HNO 3 Supercritical CO of (C) 2 Supercritical CO of fluids 2 Extracting fluid;
(3) Separation and collection of uranium-containing solution: supercritical CO 2 Supercritical CO after fluid extraction 2 Carrying uranium into a separation device in which the pressure is reduced, CO 2 Gasifying and collecting uranium-containing solution in the separation equipment.
The related principle of the invention is as follows:
pretreatment of uranium-containing alkaline residue: grinding and sieving the alkaline residue to 10-200 meshes, spreading the alkaline residue in a high-temperature resistance furnace, and setting the temperature of the high-temperature resistance furnace to be 110-150 ℃. The high-temperature resistance furnace is connected with the steam generator. Setting the temperature of the steam generator at 110-150 ℃ and the flow rate at 0.1-0.5mL/min. Opening the inlet and outlet valves of the high-temperature resistance furnace, and allowing the vapor to enter the high-temperature resistance furnace for vapor oxidation reaction. Maintaining the pressure in the high-temperature resistance furnace to be 0.2-1MPa, and maintaining for at least 2h.
Supercritical CO 2 Fluid extraction process: CO is processed by 2 The temperature of the refrigerator is set to be 0-6 ℃, the temperature of the extraction kettle and the temperature of the separation kettle are set to be 40-80 ℃, the pressure of the extraction kettle is set to be 15-25MPa, and the pressure of the separation kettle is set to be 8MPa. Accurately weighing the pretreated alkaline residue in an extraction kettle, adding 25% saturated aluminum nitrate solution, uniformly mixing, and sealing the extraction kettle; TBP-HNO is added into a carrier pump 3 ，TBP-HNO 3 And the stoichiometric ratio of uranium in the alkaline residue is 1:4-1:10. After the temperature reaches the set temperature, starting CO 2 Pump, pressurization. And after the pressure reaches the set pressure, starting the carrier pump. Carrier and liquid CO 2 Mixing, entering from the bottom of the extraction kettle, and exiting from the top. In the extraction kettle, TBP-HNO is entrained 3 Supercritical CO of complexing agent 2 Penetrating the surface of the alkaline residue and interacting with uranium to form UO 2 (NO 3 ) 2 ·2TBP。UO 2 (NO 3 ) 2 Dissolution of 2TBP in supercritical CO 2 Is covered by CO 2 And (5) taking out of the extraction kettle and entering a separation kettle. In the separation tank, UO due to pressure drop 2 (NO 3 ) 2 2TBP remains in the separation tank, CO 2 Through CO 2 The pump is circularly used after pressurizing. And opening a valve at the bottom of the separation kettle, and collecting uranium-containing solution.
In a preferred embodiment, the invention provides a method for extracting uranium in uranium-containing wastewater precipitation forming alkaline residue, wherein in the step (1), the uranium-containing wastewater precipitation forming alkaline residue is ground and sieved to 10-200 meshes, and then steam oxidation reaction is carried out.
In a preferred embodiment, the invention provides a method for extracting uranium from uranium-containing wastewater precipitation to form alkaline residue, wherein in the step (1), the temperature of the steam oxidation reaction is 110-150 ℃, the pressure is 0.2-1MPa, and the time is 2-5 hours.
In a preferred embodiment, the invention provides a method for extracting uranium from uranium-containing wastewater precipitated to form alkaline residue, wherein in the step (1), the steam oxidation reaction is performed in a resistance furnace, and the flow rate of steam is 0.1-0.5mL/min.
In a preferred embodiment, the invention provides a method for extracting uranium in uranium-containing wastewater precipitation forming alkaline residue, wherein in the step (2), the mixture mass ratio of the uranium-containing wastewater precipitation forming alkaline residue after steam oxidation reaction and the saturated aluminum nitrate solution is 20:1-4.
In a preferred embodiment, the invention provides a method for extracting uranium from uranium-containing wastewater precipitated to form alkaline residue, wherein in step (2), the TBP-HNO is used for extracting uranium from the alkaline residue 3 Is TBP saturated with nitric acid, wherein the concentration of nitric acid is 3.5-4.5mol/L.
In a preferred embodiment, the invention provides a method for extracting uranium from uranium-containing wastewater precipitated to form alkaline residue, wherein in the step (2), after the steam oxidation reaction, uranium in the alkaline residue, TBP-HNO, is precipitated relative to the uranium-containing wastewater according to a stoichiometric ratio 3 The TBP is in excess of 4-10 times.
In a preferred embodiment, the invention provides an extraction method of uranium in uranium-containing wastewater precipitation to form alkaline residue, wherein in the step (2), the supercritical extraction is performed at a temperature of 40-80 ℃, a pressure of 15-25MPa, and a time of 1-3h.
In a preferred embodiment, the invention provides a method for extracting uranium from uranium-containing wastewater precipitated to form alkaline residue, wherein in step (3), the temperature in the separation device is 40-80 ℃ and the pressure is 6-10MPa.
In a preferred embodiment, the invention provides an extraction method for uranium in alkaline residue formed by precipitation of uranium-containing wastewater, wherein in the step (2), the supercritical extraction equipment is an extraction kettle; in the step (3), the separation equipment is a separation kettle.
The method has the beneficial effects that the uranium extraction method in the alkaline residue formed by the uranium-containing wastewater precipitation can be used for extracting uranium from the alkaline residue formed by the uranium-containing wastewater precipitation with high extraction rate and low secondary waste production.
The method comprises the pretreatment of alkaline residue and supercritical CO 2 The fluid circulates and extracts two processes. Grinding the alkaline residue into powder by pretreatment, and increasing supercritical CO 2 Contact area of fluid and caustic sludge while simultaneously reducing UF in caustic sludge powder 4 All are converted into supercritical CO 2 UO of fluid extraction 2 Form of the invention. Then through TBP-HNO 3 Supercritical CO of (C) 2 The fluid extracts uranium directly from the caustic sludge powder. Supercritical CO 2 The fluid extraction technology basically realizes the operation of nonaqueous solvent, and compared with the traditional circulating dissolution and other methods, the method reduces the production of secondary waste. By pre-treatment, supercritical CO 2 Fluid circulation extraction and other processes, supercritical CO 2 The extraction efficiency of the fluid on uranium is improved to more than 99%, the uranium content in the extracted slag is less than 0.1%, and the ultra-low level radioactive waste treatment standard is met. The method does not use a strong corrosive medium and has potential industrial application value.
When the processes of cyclic dissolution, nitric acid leaching, concentrated acid curing, high-temperature roasting and the like are adopted for recycling uranium in uranium waste residues in contrast Xu Na and the like, the uranium content in the residues can be reduced to 0.059%, but the process test needs strong corrosive reagents of concentrated sulfuric acid, and only the cyclic dissolution needs 96 hours. By adopting the method of the invention, the whole process flow is not more than 8 hours, and the operation time is greatly shortened; and only a nitric acid reagent is needed, and only the nitric acid corrosion resistance of the material is needed to be considered during industrial popularization.
By supercritical CO in contrast to She Shuang and the like 2 The extraction rate of uranium in the untreated alkaline residue can reach 90%, while the invention changes the form and supercritical CO of uranium in the alkaline residue 2 And by means of cyclic extraction and the like, the extraction rate is improved to 99.5%, the uranium content in the extraction slag is reduced to 0.05%, and the extraction slag can reach the extremely low radioactive waste standard.
Detailed Description
The following examples are presented to further illustrate embodiments of the invention.
Example 1:
(1) Uranium-containing alkaline residue (which is uranium-containing wastewater generated in the uranium element manufacturing process and formed by precipitation-calcination) is screened to 10-20 meshes by an automatic screening machine, and the total amount is about 300g.
(2) Spreading the sieved alkaline residue into a enamel tray, setting the temperature of a high-temperature resistance furnace to be 110 ℃, starting a steam generator, and setting the flow to be 0.5mL/min. And opening a gas inlet valve and a gas outlet valve after the temperature of the high-temperature resistance furnace reaches the set temperature, so that the pressure in the high-temperature resistance furnace is 0.2MPa. And after 4 hours, the steam generator and the high-temperature resistance furnace are closed.
(3) Turning on supercritical CO 2 The fluid extraction device is provided with a refrigerator with the temperature of 6 ℃, and the temperatures of an extraction kettle and a separation kettle are 50 ℃; setting the pressure of the extraction kettle to 20MPa and the pressure of the separation kettle to 8MPa. 288.76g of the treated alkaline residue is accurately weighed into an extraction kettle, 58.30g of 25wt% saturated aluminum nitrate solution is added, and the upper cover of the extraction kettle is sealed. 624.37g TBP-HNO are added into a carrier tank 3 Complexing agent. Start supercritical CO 2 And (5) fluid extraction. Sampling from the separating kettle at intervals of 30min, and stopping supercritical CO after no solution flows out of the separating kettle after about 2h 2 And (5) fluid extraction.
(4) And (5) analyzing the sample. Grinding the extracted alkaline residue in the step (3) to be larger than 60 meshes by an automatic grinder, then taking 3g of the extracted alkaline residue according to a quartering method, and analyzing the content of residual uranium in the extracted alkaline residue by adopting an ammonium bifluoride full-dissolution method (a dissolution method of reference uranium ore). The uranium content in the original caustic sludge is 9.6wt% to obtain supercritical CO 2 The extraction efficiency of the fluid on uranium in the alkaline residue is 99.5%, and the content of uranium in the extracted alkaline residue is less than 0.05%.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. The foregoing examples or embodiments are merely illustrative of the invention, which may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims are intended to be encompassed within the scope of the invention.
Claims (5)
1. The extraction method for uranium in the alkaline residue formed by precipitation of uranium-containing wastewater is characterized by comprising the following steps of:
(1) Pretreatment of uranium-containing alkaline residue: precipitating the uranium-containing wastewater to form alkaline residue for steam oxidation reaction; the steam oxidation reaction is carried out in a resistance furnace, the reaction temperature is 110-150 ℃, the pressure is 0.2-1MPa, the time is 2-5 hours, and the flow rate of the introduced steam is 0.1-0.5mL/min;
(2) Supercritical CO 2 Fluid extraction: in supercritical CO 2 In fluid extraction equipment, the uranium-containing wastewater after the water vapor oxidation reaction is precipitated to form alkaline residue, and the alkaline residue is mixed with saturated aluminum nitrate solution and then is introduced into a reactor containing TBP-HNO 3 Supercritical CO of (C) 2 Supercritical CO of fluids 2 Fluid extraction, wherein the temperature of supercritical extraction is 40-80 ℃, the pressure is 15-25MPa, and the time is 1-3h; the mixed mass ratio of the alkaline residue formed by the uranium-containing wastewater sediment after the steam oxidation reaction and the saturated aluminum nitrate solution is 20:1-4; the TBP-HNO3 is TBP saturated with nitric acid, wherein the concentration of the nitric acid is 3.5-4.5mol/L; after the steam oxidation reaction, according to stoichiometric ratio, precipitating uranium in alkaline residue relative to uranium-containing wastewater to form 4-10 times of TBP in TBP-HNO 3;
(3) Separation and collection of uranium-containing solution: supercritical CO 2 Supercritical CO after fluid extraction 2 Carrying uranium into a separation device in which the pressure is reduced, CO 2 Gasifying and collecting uranium-containing solution in the separation equipment.
2. The extraction method according to claim 1, characterized in that: in the step (1), the uranium-containing wastewater is precipitated to form alkaline residue, ground and sieved to 10-200 meshes, and then steam oxidation reaction is carried out.
3. The extraction method according to claim 1, characterized in that: in the step (3), the temperature in the separation equipment is 40-80 ℃ and the pressure is 6-10MPa.
4. The extraction method according to claim 1, characterized in that: in the step (2), the supercritical extraction equipment is an extraction kettle.
5. The extraction method according to claim 1, characterized in that: in the step (3), the separation equipment is a separation kettle.
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Citations (3)
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|---|---|---|---|---|
| CN102534270A (en) * | 2011-12-27 | 2012-07-04 | 南华大学 | Multifunctional CO2 uranium leaching device |
| CN102936655A (en) * | 2011-08-16 | 2013-02-20 | 中国核动力研究设计院 | Technology for recovery of uranium in ceramic UO2 pellet by supercritical CO2 extraction |
| CN104060112A (en) * | 2014-06-25 | 2014-09-24 | 南华大学 | Method for leaching uranium from low-grade uranium ores by utilizing supercritical carbon dioxide |
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| US7128840B2 (en) * | 2002-03-26 | 2006-10-31 | Idaho Research Foundation, Inc. | Ultrasound enhanced process for extracting metal species in supercritical fluids |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936655A (en) * | 2011-08-16 | 2013-02-20 | 中国核动力研究设计院 | Technology for recovery of uranium in ceramic UO2 pellet by supercritical CO2 extraction |
| CN102534270A (en) * | 2011-12-27 | 2012-07-04 | 南华大学 | Multifunctional CO2 uranium leaching device |
| CN104060112A (en) * | 2014-06-25 | 2014-09-24 | 南华大学 | Method for leaching uranium from low-grade uranium ores by utilizing supercritical carbon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| 超临界CO2流体从高品位铀废渣中萃取铀的实验研究;叶爽;《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》(第1期);B014-1533 * |
| 连培生.《原子能工业》.原子能出版社,2002,227. * |
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