CN117735497A - Defluorination purification method for uranyl nitrate solution containing fluorine - Google Patents
Defluorination purification method for uranyl nitrate solution containing fluorine Download PDFInfo
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- CN117735497A CN117735497A CN202211112607.XA CN202211112607A CN117735497A CN 117735497 A CN117735497 A CN 117735497A CN 202211112607 A CN202211112607 A CN 202211112607A CN 117735497 A CN117735497 A CN 117735497A
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- Prior art keywords
- nitrate solution
- uranyl nitrate
- uranium
- ammonium
- fluorine
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- 229910002007 uranyl nitrate Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 238000000746 purification Methods 0.000 title claims abstract description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 4
- 238000006115 defluorination reaction Methods 0.000 title description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- -1 ammonium uranium tricarbonate Chemical compound 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 16
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 claims abstract description 10
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000005289 uranyl group Chemical group 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 abstract description 16
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003758 nuclear fuel Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- MZFRHHGRNOIMLW-UHFFFAOYSA-J uranium(4+);tetrafluoride Chemical compound F[U](F)(F)F MZFRHHGRNOIMLW-UHFFFAOYSA-J 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of nuclear fuel circulation, in particular to a method for removing fluorine from a uranyl nitrate solution containing fluorine. The method for removing fluorine from the uranyl nitrate solution comprises the following steps: fully dissolving the fluorinated slag to obtain uranyl nitrate solution; adding ammonia water into the uranyl nitrate solution, adjusting the pH value to 2-3, adding ammonium carbonate until the pH value of the solution is 8-9, and aging; performing solid-liquid separation on the aged product, and washing an ammonium uranate filter cake by using an ammonium carbonate solution; and (5) heating and decomposing the washed ammonium uranium tricarbonate filter cake to obtain uranium dioxide. The invention realizes the purification of fluoride ions in uranyl nitrate solution and improves the recycling of uranium in the uranium conversion process.
Description
Technical Field
The invention relates to the technical field of nuclear fuel circulation, in particular to a method for removing fluorine from a uranyl nitrate solution containing fluorine.
Background
In the process of preparing uranium hexafluoride by converting natural uranium with a vertical fluorination reactor as a key device, a certain amount of fluorinated slag is inevitably generated, and the main components of the fluorinated slag are intermediate fluorides of uranium, uranium tetrafluoride, fluorides of other metal impurities, and the like. The uranium content level is higher, recycling of uranium in the fluoridized slag can be achieved, and obvious economic benefits are achieved. However, the content of fluoride ions in the hydrolysate of the fluoridized slag is up to 140g/L.
If uranium in the fluoride slag is recovered in the form of uranyl nitrate, a certain amount of fluoride ions are necessarily present in the generated uranyl nitrate solution, and the presence of the fluoride ions has a remarkable influence on the TBP extraction and back extraction process of the uranyl nitrate solution; meanwhile, the removal of fluoride ions can seriously affect the butt joint of a fluorinated slag treatment process system and the existing uranium purification and conversion production line.
Disclosure of Invention
The invention aims to solve the technical problems that: the method for removing fluorine from the uranyl nitrate solution realizes the purification of fluoride ions in the uranyl nitrate solution, and improves the recycling of uranium in the uranium conversion process.
The invention provides a defluorination purification method of a fluorine-containing uranyl nitrate solution, which comprises the following steps:
step one: fully dissolving the fluorinated slag to obtain uranyl nitrate solution;
step two: adding ammonia water into the uranyl nitrate solution, adjusting the pH value to 2-3, adding ammonium carbonate until the pH value of the solution is 8-9, and aging;
step three: performing solid-liquid separation on the aged product, and washing an ammonium uranate filter cake by using an ammonium carbonate solution;
step four: and (5) heating and decomposing the washed ammonium uranium tricarbonate filter cake to obtain uranium dioxide.
Preferably, the first step is specifically:
dissolving the fluorinated slag with deionized water, then adding nitric acid to obtain uranyl nitrate solution and solid insoluble matters, and filtering to remove the solid insoluble matters.
Preferably, in the second step, ammonia water is added while stirring is continued.
Preferably, in the second step, the aging time is 2 to 5 hours.
Preferably, in the third step, the ammonium carbonate solution is used for washing the ammonium uranate tricarbonate filter cake for 3-5 times.
Preferably, in the third step, the concentration of the ammonium carbonate solution is 1mol/L.
Preferably, in the fourth step, the heating temperature is 550 to 650 ℃.
Compared with the prior art, the fluorine-removing purification method of the fluorine-containing uranyl nitrate solution comprises the steps of firstly dissolving fluoride residues to remove insoluble substances, and then precipitating uranium by utilizing ammonium carbonate to realize the separation of metal impurities and uranium; the precipitated uranyl ammonium tricarbonate is heated to be converted into uranium dioxide, and can be used as a raw material of a hydrofluorination process for preparing an intermediate product of uranium tetrafluoride, so that the purposes of removing fluoride ions from fluorinated residues and recycling metal uranium are achieved. The method has simple flow, is practical and feasible, is easy to realize industrial application, and has obvious economic benefit and environmental protection benefit.
Drawings
Fig. 1 shows a flow chart of a method for defluorination and purification of a uranyl nitrate solution containing fluorine.
Detailed Description
For a further understanding of the present invention, embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the invention.
The embodiment of the invention discloses a method for removing fluorine from a uranyl nitrate solution containing fluorine, which is shown in figure 1 and comprises the following steps:
step one: fully dissolving the fluorinated slag to obtain uranyl nitrate solution;
step two: adding ammonia water into the uranyl nitrate solution, adjusting the pH value to 2-3, adding ammonium carbonate until the pH value of the solution is 8-9, and aging;
step three: performing solid-liquid separation on the aged product, and washing an ammonium uranate filter cake by using an ammonium carbonate solution;
step four: and (5) heating and decomposing the washed ammonium uranium tricarbonate filter cake to obtain uranium dioxide.
The method for purifying fluorine-containing uranyl nitrate solution according to the present invention is described in detail below according to the steps:
step one: and (3) fully dissolving the fluorinated slag to obtain uranyl nitrate solution.
The first step is specifically as follows:
dissolving the fluorinated slag with deionized water, then adding nitric acid to obtain uranyl nitrate solution and solid insoluble matters, and filtering to remove the solid insoluble matters.
Step two: adding ammonia water into the uranyl nitrate solution, continuously stirring while adding the ammonia water, adjusting the pH value to 2-3, adding ammonium carbonate solid until the pH value of the solution is 8-9, and aging.
The aging time is preferably 2 to 5 hours, more preferably 3 hours.
Step three: and (3) carrying out solid-liquid separation on the aged product, and washing an ammonium uranate filter cake by using an ammonium carbonate solution.
And washing the ammonium uranyl tricarbonate filter cake (AUC) 3-5 times by using an ammonium carbonate solution.
The concentration of the ammonium carbonate solution is 1mol/L.
Step four: and (5) heating and decomposing the washed ammonium uranium tricarbonate filter cake to obtain uranium dioxide.
In view of the fact that AUC contains a certain amount of fluoride ions, the heating temperature is preferably 550 to 650 ℃, more preferably 600 ℃.
The microwave dryer or the rotary kiln device is used as key equipment, and the prepared uranyl ammonium tricarbonate is heated at the temperature of about 600 ℃. Under the action of gaseous product ammonia, uranium dioxide can be produced.
Uranium dioxide can be used as a raw material of a hydrofluorination process for preparing an intermediate product of uranium tetrafluoride, so that the purposes of removing fluoride ions from fluorinated slag and recycling metallic uranium are achieved.
In order to further understand the present invention, the following description will be given in detail with reference to examples for purifying uranyl nitrate solution containing fluorine, and the scope of protection of the present invention is not limited by the following examples.
Example 1
After adding water and nitric acid into the fluorinated residues to be fully dissolved, delivering the uranyl nitrate solution obtained after dissolution to a centrifugal separator to realize separation of the uranyl nitrate solution and insoluble solids. Delivering uranyl nitrate solution to an AUC precipitation tank, adding ammonia water, starting the AUC precipitation tank to mechanically stir, adjusting the pH value of the solution to 2-3, adding ammonium carbonate solid into the solution until the pH value of the solution reaches 8-9, stopping mechanical stirring, and aging for 3 hours. And conveying the prepared AUC precipitate to a centrifugal separator to realize solid-liquid separation of the AUC precipitate, stopping adding the AUC turbid liquid after a certain amount of solid in the centrifugal separator is reached, introducing 1mol/L ammonium carbonate solution into the centrifugal separator, and repeatedly washing the generated AUC filter cake for 3 times to further remove impurities and fluoride ions carried in the AUC.
2. The washed AUC filter cake enters a feeding hopper of a microwave heater or a rotary furnace, and is sent into a front zone of the microwave heater or the rotary furnace through a screw conveyor. Under the rotation of the furnace cylinder, the material moves towards the furnace tail along the furnace cylinder, and simultaneously, the furnace wall reaction temperature is controlled to be 600 ℃, the decomposition reaction and the reduction reaction are successively completed to be converted into uranium dioxide, and the uranium dioxide can be used as a raw material for a hydrofluorination process and used for preparing a uranium tetrafluoride intermediate product, so that fluoride ions are removed from fluorinated slag and metal uranium is recovered.
The fluoride ion purifying efficiency can reach 90.7%, and the uranium recovery rate can reach 87.5%.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The method for removing and purifying the fluorine-containing uranyl nitrate solution is characterized by comprising the following steps of:
step one: fully dissolving the fluorinated slag to obtain uranyl nitrate solution;
step two: adding ammonia water into the uranyl nitrate solution, adjusting the pH value to 2-3, adding ammonium carbonate until the pH value of the solution is 8-9, and aging;
step three: performing solid-liquid separation on the aged product, and washing an ammonium uranate filter cake by using an ammonium carbonate solution;
step four: and (5) heating and decomposing the washed ammonium uranium tricarbonate filter cake to obtain uranium dioxide.
2. The method for fluorine removal purification of a uranyl nitrate solution containing fluorine according to claim 1, wherein the first step is specifically:
dissolving the fluorinated slag with deionized water, then adding nitric acid to obtain uranyl nitrate solution and solid insoluble matters, and filtering to remove the solid insoluble matters.
3. The method for fluorine removal purification of a uranyl nitrate solution according to claim 1, wherein in the second step, ammonia water is added while continuing stirring.
4. The method for fluorine removal purification of a uranyl nitrate solution according to claim 1, wherein in the second step, the aging time is 2 to 5 hours.
5. The method for fluorine removal purification of a uranyl nitrate solution according to claim 1, wherein in the third step, the ammonium carbonate solution is used to wash the ammonium uranyl tricarbonate filter cake 3 to 5 times.
6. The method for fluorine removal purification of a uranyl nitrate solution according to claim 5, wherein in the third step, the concentration of the ammonium carbonate solution is 1mol/L.
7. The method for fluorine removal purification of a uranyl nitrate solution according to claim 1, wherein in the fourth step, the heating temperature is 550 to 650 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211112607.XA CN117735497A (en) | 2022-09-14 | 2022-09-14 | Defluorination purification method for uranyl nitrate solution containing fluorine |
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| CN202211112607.XA CN117735497A (en) | 2022-09-14 | 2022-09-14 | Defluorination purification method for uranyl nitrate solution containing fluorine |
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| CN117735497A true CN117735497A (en) | 2024-03-22 |
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| CN202211112607.XA Pending CN117735497A (en) | 2022-09-14 | 2022-09-14 | Defluorination purification method for uranyl nitrate solution containing fluorine |
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- 2022-09-14 CN CN202211112607.XA patent/CN117735497A/en active Pending
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