CN114506819B - Process for removing uranium from hydrofluoric acid solution - Google Patents
Process for removing uranium from hydrofluoric acid solution Download PDFInfo
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- CN114506819B CN114506819B CN202011288705.XA CN202011288705A CN114506819B CN 114506819 B CN114506819 B CN 114506819B CN 202011288705 A CN202011288705 A CN 202011288705A CN 114506819 B CN114506819 B CN 114506819B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 138
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 title abstract description 21
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 107
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- -1 hydrofluoric acid uranium Chemical compound 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 52
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FEXVSRAUZDRPMZ-UHFFFAOYSA-F [F-].[Ca+2].[U+6].[F-].[F-].[F-].[F-].[F-].[F-].[F-] Chemical compound [F-].[Ca+2].[U+6].[F-].[F-].[F-].[F-].[F-].[F-].[F-] FEXVSRAUZDRPMZ-UHFFFAOYSA-F 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- VZFAZKACJSVHPW-UHFFFAOYSA-L calcium hydron trifluoride Chemical compound [H+].[F-].[F-].[F-].[Ca++] VZFAZKACJSVHPW-UHFFFAOYSA-L 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005388 cross polarization Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007614 genetic variation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000783 metal toxicity Toxicity 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003671 uranium compounds Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/197—Separation; Purification by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application researches a process for removing uranium from hydrofluoric acid solution, which takes the uranium-containing hydrofluoric acid solution as a research object, and modifies calcium fluoride by a tunnel type industrial microwave method so as to remove uranium in the hydrofluoric acid solution. The method can reduce the concentration of uranium in hydrofluoric acid, does not introduce other ions, and does not pollute hydrofluoric acid solution; the whole process is low in cost, less in three wastes, environment-friendly, simple to operate and easy to realize, and achieves the purposes of removing uranium from hydrofluoric acid solution and recycling hydrofluoric acid, and the uranium removal rate of the process reaches more than 95%. In the process, the selected calcium fluoride is cheap and easy to obtain, and the modified calcium fluoride has potential value of large-scale application.
Description
Technical Field
The application belongs to the technical field of uranium hydrometallurgy, and particularly relates to a process for removing uranium, in particular to a process for removing uranium from hydrofluoric acid solution.
Background
Hydrofluoric acid is an aqueous solution of hydrogen fluoride gas, is a clear, colorless, fuming, corrosive liquid, and has a severe pungent odor. Hydrofluoric acid is an important production raw material for fluoridation, and has wide application in the fields of electronics, metallurgy, chemical industry, light industry, pesticides, daily use, construction, military and the like. Hydrofluoric acid can be used for producing refrigerants, chemical derivatives, aluminum manufacturing, petroleum alkylation catalysts and the like; because hydrofluoric acid has strong corrosiveness, the method can be used for pickling, etching and the like of stainless steel.
Uranium is an element with an atomic number of 92, and its element symbol is U, which is the heaviest element found in nature. Three isotopes exist in nature, all of which have radioactivity and possess very long half-lives (tens of thousands to 45 hundred million years). The uranium atomic energy generates fission reaction and releases a large amount of energy, so that the nuclear magnetic resonance nuclear power generation device can be applied to the fields of power generation, nuclear weapon manufacturing and the like. The nuclear weapon program of the second world allied forces triggers the demand for uranium, the production of which is established. By the 70 s of the 20 th century, the uranium production industry has been firmly established. From this point on, scientific research and production of uranium are receiving great attention from countries around the world, and the nuclear weapon manufacturing and nuclear power generation industries are rapidly developing. The uranium industry in china has emerged from the 50 s of the 20 th century as a complete and fairly large scale scientific and industrial production system.
In the hydrometallurgical process of uranium, hydrofluoric acid is a common reagent, and products UF4 and UF6 are important uranium compounds. From uranium ore, UF4 may be prepared by a wet process, i.e. in aqueous solution, by reduction and precipitation, to produce nuclear purity grade UF4. The processes all generate a certain amount of uranium-containing hydrofluoric acid byproducts, and hydrofluoric acid is generally stored in a tank in a production field, has corrosiveness, is in leakage risk after long-term storage, can harm animal and plant life, and has influence on the environment and the public. While uranium, even very low radiation, can endanger human health, cause cancer, and even cause genetic variation; in the case of heavy metal toxicity, such toxicity occurs after entering the human body, such as respiration, drinking water, etc. Uranium also causes various cancers, chronic poisoning and physical lesions as well as other heavy metal elements such as lead, cadmium, arsenic. For the reasons, the uranium removal and the treatment of uranium-containing solutions and the recycling of the solutions thereof are troublesome problems which are currently required to be solved by human beings.
The traditional method adopts a chemical precipitation method, an evaporation concentration method, an ion exchange method, various coals, an adsorbent adsorption method and the like to directly remove uranium in uranium-containing water body by adjusting the acid-base of the solution, but has certain problems such as high cost, secondary treatment of the product and the like. The nuclear waste is safely returned to nature, and on the basis of the traditional purification treatment, the used reagent, such as hydrofluoric acid, is purified and recycled, so that the method not only accords with the concept of green and environment protection, but also is a new uranium removal idea. Therefore, the method can recycle the required substances and achieve the aim of removing uranium, and more importantly, the product does not need to be subjected to secondary treatment, so that the method is cost-saving and environment-friendly.
In the traditional industry, the uranium-containing hydrofluoric acid uranium removal method is to add a modified carbon material into a solution and then heat the solution to 240-300 ℃. The adsorption capacity of the carbon material is utilized to remove uranium in the solution, the removal rate is low, and the removal rate can only reach 42% -64%, so that the purposes of removing uranium and recycling hydrofluoric acid can not be achieved.
Therefore, how to remove uranium from hydrofluoric acid solution and recycle high-purity hydrofluoric acid is a considerable problem.
Disclosure of Invention
In order to overcome the problems, the inventor has conducted intensive research and research into a process for removing uranium from a hydrofluoric acid solution, wherein the process takes the uranium-containing hydrofluoric acid solution as a research object, and the process modifies calcium fluoride by a tunnel type industrial microwave method so as to remove uranium in the hydrofluoric acid solution. The method can reduce the concentration of uranium in hydrofluoric acid, does not introduce other ions, and does not pollute hydrofluoric acid solution; the whole process is low in cost, less in three wastes, environment-friendly, simple to operate and easy to realize, and achieves the purposes of removing uranium from hydrofluoric acid solution and recycling hydrofluoric acid better, and the uranium removal rate of the process reaches more than 95%. In the process, the selected calcium fluoride is cheap and easy to obtain, and the modified calcium fluoride has potential value of large-scale application, so that the application is completed.
In particular, it is an object of the present application to provide the following aspects:
in a first aspect, a modified calcium fluoride is provided, which is prepared by treating ordinary calcium fluoride by a microwave method.
Wherein the modified calcium fluoride is prepared by a process comprising the steps of:
and step 1, ball milling and sieving common calcium fluoride.
And 2, treating the screened calcium fluoride by a microwave method.
Wherein in the step 1, the calcium fluoride after sieving has a particle size of 200 meshes or less and a ratio of 50% or more.
In the step 2, the frequency range of the microwaves is 1.50-3.00GHz.
In a second aspect, a uranium-containing hydrofluoric acid uranium removal method is provided, wherein modified calcium fluoride after microwave treatment is adopted to carry out uranium removal treatment on the uranium-containing hydrofluoric acid.
Wherein the method comprises the steps of:
and step I, preparing the modified calcium fluoride.
And II, adding the calcium fluoride subjected to microwave treatment into uranium-containing hydrofluoric acid solution, stirring, and carrying out solid-liquid separation.
Wherein the specific surface area of the modified calcium fluoride is 16m 2 And/g.
In the step II, the weight ratio of the added modified calcium fluoride to uranium in the hydrofluoric acid solution is 15% -55%.
In the step II, the stirring is mechanical stirring, and the stirring time is more than 3 hours.
In a third aspect, there is provided the use of the modified calcium fluoride of the first aspect for the treatment of a radiocontaminated solution, preferably a uranium containing hydrofluoric acid solution.
The application has the beneficial effects that:
(1) The method utilizes the calcium fluoride, is low in cost and easy to obtain, has large specific surface area after modification, has large-scale application value, effectively removes uranium in the hydrofluoric acid, does not introduce other ions into the hydrofluoric acid, has the uranium removal rate of more than 95%, and achieves good effects.
(2) According to the application, the uranium-containing hydrofluoric acid solution is used as a raw material, and the calcium fluoride is modified by a microwave method, so that uranium in the hydrofluoric acid solution is removed.
(3) The microwave method equipment used in the application is a tunnel microwave oven, can realize mode distribution and excellent heating uniformity, has a perfect locking protection system, can continuously and stably work for a long time, is convenient to operate, and reduces energy consumption.
(4) In the process, the links of heating and the like in the traditional treatment method are eliminated, the cost is reduced, and the method is environment-friendly.
Detailed Description
The present application will be described in further detail by means of preferred embodiments. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In a first aspect of the present application, there is provided a modified calcium fluoride treated by microwave method to improve the specific surface area of calcium fluoride.
Wherein, the radioactive element uranium in the hydrofluoric acid solution is treated with calcium fluoride because of the special use thereof, and the content of the common calcium fluoride is more than 90%, preferably more than 95%, more preferably more than 98.5%.
In the application, in view of the characteristics of excellent specific surface area and stable chemical property of the calcium fluoride powder, the uranium-removing purpose of the application is achieved by utilizing a method of adsorption coprecipitation of uranium-containing hydrofluoric acid calcium fluoride. The specific surface area of common calcium fluoride in the market is not large, and the requirements of the process cannot be met, so that the calcium fluoride needs to be further modified.
In the application, the specific surface area of the modified calcium fluoride is 16m 2 Preferably at least 18m 2 Above/g, more preferably at 20m 2 And/g. The larger the specific surface area of the modified calcium fluoride is, the more complete the contact between the modified calcium fluoride and uranium-containing hydrofluoric acid solution to be treated is, so that the more complete the reaction and the more thorough the coprecipitation is; on the other hand, if the specific surface area of calcium fluoride is too small, thenThe uranium-containing calcium fluoride slag of the product after the reaction is likely to adhere to the surface of the calcium fluoride so as to prevent the contact between the modified calcium fluoride and uranium in the uranium-containing hydrofluoride solution, further preventing the reaction from proceeding, and resulting in incomplete uranium removal.
In the present application, considering that microwaves can penetrate into the interior of a substance, not by means of heat conduction of the substance itself; meanwhile, the whole heating process can be completed in a short time; the application has the advantages of high heat energy utilization rate, energy saving, no pollution and contribution to improving labor conditions, and the application is preferably used for modifying common calcium fluoride by a microwave method.
The equipment of the microwave method is a microwave oven, preferably a tunnel type industrial microwave oven. The tunnel type industrial microwave oven is a variation of large-scale microwave oven, and is characterized by that the oven bodies of microwave oven are connected in series to make them become tunnel oven, on the other hand the turntable of microwave oven is reformed into repeatedly-running conveying belt. The tunnel microwave oven distributes energy to the microwave heating box body in multiple groups through the cross polarization mode, and the microwave heating box body is distributed to multiple slots respectively, so that mode distribution and excellent heating uniformity can be achieved, a perfect locking protection system is provided, continuous and stable operation can be realized for a long time, energy consumption is reduced, operation is convenient, and meanwhile, the requirement of large production capacity can be met.
In a further preferred embodiment, the modified calcium fluoride is prepared by a process comprising the steps of:
and step 1, ball milling and sieving common calcium fluoride.
Wherein the calcium fluoride content is 90% or more, preferably 95% or more, more preferably 98.5% or more.
In order to mix the calcium fluoride and the uranium-containing hydrofluoric acid solution to be treated more uniformly and remove uranium more thoroughly, the dispersity of the calcium fluoride needs to be improved and the granularity needs to be reduced.
In the present application, preferably, the calcium fluoride is ball milled to achieve the above object.
Wherein the calcium fluoride after sieving has a particle size of 200 mesh or less of 50% or more, preferably 60% or more, more preferably 70% or more.
In the application, the inventor researches and discovers that in the ball milling process, the granularity of the calcium fluoride powder is controlled, and the proper granularity is controlled, so that the mud caused by excessive crushing is avoided, and the energy consumption is reduced. The inventor has proved by a large number of practices that the proportion of the screened calcium fluoride below 200 meshes is more than 50%, especially more than 70%, so that a better uranium removal effect can be achieved.
And 2, treating the screened calcium fluoride by a microwave method.
Wherein, the equipment of the microwave method is a microwave oven, preferably a tunnel type industrial microwave oven.
Wherein the frequency of the microwaves ranges from 1.50 GHz to 3.00GHz, preferably from 1.80 GHz to 2.80GHz, more preferably from 2.30 GHz to 2.60GHz, for example from 2.45GHz, and the time of the microwaves ranges from 1 min to 12min, preferably from 4 min to 10min, more preferably from 7 min to 9min.
In the application, the inventor researches and discovers that when the microwave method is used for modifying the calcium fluoride, the microwave frequency is 2.30-2.60GHz, and the time is 7-9min, the calcium fluoride has large specific surface area, so that the aim of thoroughly removing uranium is fulfilled.
The preparation method of the modified calcium fluoride provided by the application has the advantages of simple operation, energy consumption saving, large specific surface area and even 20m 2 And the capacity of treating uranium-containing waste liquid is higher than/g.
In a second aspect of the application, a uranium-containing hydrofluoric acid uranium removal method is provided, wherein uranium-containing hydrofluoric acid is subjected to uranium removal treatment by modified calcium fluoride after microwave treatment. According to a preferred embodiment of the application, the uranium-bearing hydrofluoric acid solution uranium removal treatment method comprises the following steps:
and step I, preparing modified calcium fluoride.
Wherein the modified calcium fluoride can be the modified calcium fluoride according to the first aspect, and the specific surface area of the modified calcium fluoride is 16m 2 Preferably at least 18m 2 Above/g, more preferably at 20m 2 And/g.
In the application, the uranium in the hydrofluoric acid solution is treated by the calcium fluoride, and the calcium fluoride has the advantages of excellent specific surface area and stable chemical property, so that more importantly, the calcium fluoride does not introduce new anions, the cost of subsequent further treatment is saved, and the energy consumption is reduced.
And II, adding the calcium fluoride subjected to microwave treatment into uranium-containing hydrofluoric acid solution, stirring, and carrying out solid-liquid separation.
In the application, the uranium-containing hydrofluoric acid solution has a uranium concentration range of 40-120 mg/L and a hydrofluoric acid concentration range of 20-50 g/L.
In the application, when the weight concentration of uranium in uranium-containing wastewater is lower than 40mg/L, the precipitation efficiency is reduced and the uranium removal effect is poor because of the extremely low uranium concentration; when the weight concentration of uranium in the uranium-containing wastewater is higher than 120mg/L, the uranium removal rate is reduced beyond the treatment capacity of the modified calcium fluoride.
According to a preferred embodiment of the application, the weight ratio of the added modified calcium fluoride to uranium in the hydrofluoric acid solution is 15% -55%.
In the application, calcium fluoride is slightly soluble in dilute inorganic acid, has excellent mechanical and environmental stability, modified calcium fluoride is added into hydrofluoric acid solution containing uranium and stirred, and as the calcium fluoride is slightly soluble in the hydrofluoric acid solution, calcium fluoride precipitation is separated out from the hydrofluoric acid solution when the modified calcium fluoride is added into the hydrofluoric acid solution containing uranium, and substances coexisting with uranium are caused to precipitate together, namely: uranium can coprecipitate into calcium fluoride to form uranium-containing calcium fluoride slag, and at the moment, the uranium-containing calcium fluoride slag and hydrofluoric acid liquid are separated further under the action of gravity.
In the present application, the rate at which uranium and calcium fluoride form a coprecipitate increases as the amount of calcium fluoride to be administered increases, and the weight at which the coprecipitate is formed also increases as the amount of calcium fluoride to be administered increases. The weight increases gradually with the calcium fluoride input, the coprecipitation speed increases gradually, and the coprecipitation weight increases slowly. Preferably, when the weight ratio of the modified calcium fluoride to uranium in the uranium-containing hydrofluoric acid solution is 15% -55%, the coprecipitation speed and the coprecipitation weight are optimal, that is, the uranium removal effect is optimal.
According to a preferred embodiment of the application, the stirring is mechanical stirring. The stirring time is 3 hours or more, preferably 5 hours or more, more preferably 8 to 24 hours, for example 16 hours.
In the application, stirring promotes the generation of coprecipitated uranium calcium fluoride slag, and the inventor researches that when the stirring time is less than 8 hours, especially less than 3 hours, uranium in uranium-containing hydrofluoric acid and calcium fluoride react insufficiently, so that uranium is not completely precipitated, and the uranium removal effect is poor. And when the stirring time is 8-24 hours, the uranium removing effect of the uranium-containing hydrofluoric acid solution is optimal.
After stirring, filtering to realize solid-liquid separation.
The uranium-containing hydrofluoric acid uranium removal method provided by the application is simple to operate, is suitable for the treatment of uranium-containing hydrofluoric acid with high concentration, has the uranium removal rate of more than 95% in the uranium-containing hydrofluoric acid solution, and simultaneously does not introduce other ions into the hydrofluoric acid solution.
In the application, the uranium removal rate in the uranium-containing hydrofluoric acid solution is up to more than 95%, and the hydrofluoric acid can be recycled.
In a third aspect of the application there is provided the use of the modified calcium fluoride of the first aspect for the treatment of a radioactively contaminated solution, preferably a uranium containing hydrofluoric acid solution.
Wherein the concentration of uranium in the uranium-containing wastewater is 40-120 mg/L; the concentration of hydrofluoric acid is 20-50 g/L.
Examples
The application is further described below by means of specific examples, which are however only exemplary and do not constitute any limitation on the scope of protection of the application.
The common calcium fluoride is solar brand analytically pure calcium fluoride reagent produced by Tianjin far chemical reagent limited company, and batch number 2016, year 01 and month 1026.
Example 1
Preparation of modified calcium fluoride:
(1) A200 g sample of ordinary calcium fluoride was taken, which had a calcium fluoride content of 99.2% and a specific surface area of about 15.2m2/g. Ball milling and sieving, wherein the calcium fluoride after sieving has the particle diameter of below 200 meshes and the proportion of 82%;
(2) Treating the calcium fluoride screened in the step (1) by using a tunnel type industrial microwave oven, wherein the frequency of microwaves is 2.45GHz, and the time is 8min, so that the modified calcium fluoride can be obtained. The specific surface area of the treated calcium fluoride reaches 28.0m 2 /g。
Example 2
Preparation of modified calcium fluoride:
(1) A50 g sample of ordinary calcium fluoride was taken, which had a calcium fluoride content of 98.7% and a specific surface area of about 15.0m 2 And/g. Ball milling and sieving, and CaF after sieving 2 The particle diameter is less than 200 meshes and the proportion is 93 percent;
(2) Treating the calcium fluoride screened in the step (1) by using a tunnel type industrial microwave oven, wherein the frequency of microwaves is 2.45GHz, and the time is 9min, so that the modified calcium fluoride can be obtained. Post-treatment CaF 2 The specific surface area reaches 34.2m 2 /g。
Example 3
Treatment of uranium-containing hydrofluoric acid solution:
(1) The source of the uranium-containing wastewater is self-configuration, and the configuration source is obtained by dissolving uranium-containing solid yellow cakes with acid and then further diluting, wherein the concentration of hydrofluoric acid is 32.0g/L, and the concentration of uranium is 45.0mg/L.
(2) Modified calcium fluoride was prepared as described in example 1;
(3) 1000mL of the uranium-containing calcium fluoride solution is taken, 18.2mg of prepared modified calcium fluoride is added, the weight ratio of the added calcium fluoride to uranium in the uranium-containing hydrofluoric acid solution is 40.4%, the reaction is carried out for 12h under mechanical stirring, and solid-liquid separation is realized through filtration.
Example 4
Treatment of uranium-containing hydrofluoric acid solution:
(1) The concentration of hydrofluoric acid in the uranium-containing wastewater is 26.0g/L, and the concentration of uranium is 52.0mg/L.
(2) Modified calcium fluoride was prepared as described in example 2;
(3) 800mL of the uranium-containing calcium fluoride solution is taken, 18.7mg of prepared modified calcium fluoride is added, the weight ratio of the added calcium fluoride to uranium in the uranium-containing hydrofluoric acid solution is 45.0%, the mixture is reacted for 16h under mechanical stirring, and solid-liquid separation is realized through filtration.
Example 5
The method for treating uranium-containing hydrofluoric acid solution in this example was the same as that in example 3, except that in step (1), the concentration of hydrofluoric acid in uranium-containing wastewater was 40.0g/L.
Example 6
The method for treating uranium-containing hydrofluoric acid solution in this example was the same as that in example 3, except that in step (1), the concentration of hydrofluoric acid in uranium-containing wastewater was 50.0g/L.
Example 7
The method for treating uranium-containing hydrofluoric acid solution in this example was the same as that in example 3, except that in step (1), the concentration of uranium in uranium-containing wastewater was 80.0mg/L.
Example 8
The method for treating uranium-containing hydrofluoric acid solution in this example was the same as that in example 3, except that in step (1), the concentration of uranium in the uranium-containing wastewater was 120.0mg/L.
Experimental example
The uranium concentrations in the solutions after the treatment in examples 3 to 8 were measured, and the results are shown in table 1.
TABLE 1 uranium-containing hydrofluoric acid solution uranium concentration before and after treatment and uranium removal rate
The application has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present application and do not limit the scope of the present application in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present application and its embodiments without departing from the spirit and scope of the present application, which all fall within the scope of the present application. The scope of the application is defined by the appended claims.
Claims (2)
1. The uranium-containing hydrofluoric acid uranium removal method is characterized by comprising the steps of carrying out uranium removal treatment on uranium-containing hydrofluoric acid by adopting modified calcium fluoride subjected to microwave treatment, wherein the modified calcium fluoride is prepared by treating common calcium fluoride by a microwave method;
the modified calcium fluoride is prepared by a method comprising the steps of:
step 1, ball milling and sieving common calcium fluoride, wherein the calcium fluoride after sieving has the granularity of below 200 meshes and the proportion of above 70%;
step 2, treating the screened calcium fluoride by a microwave method, wherein the frequency range of microwaves is 1.50-3.00GHz, and the time of the microwaves is 1-12min;
the uranium removing method of uranium-containing hydrofluoric acid comprises the following steps:
step I, preparing modified calcium fluoride, wherein the specific surface area of the modified calcium fluoride is 20m 2 /g or more;
step II, adding the calcium fluoride subjected to microwave treatment into a uranium-containing hydrofluoric acid solution, stirring for 8-24 hours, and carrying out solid-liquid separation, wherein in the step II, the weight ratio of the added modified calcium fluoride to uranium in the hydrofluoric acid solution is 15% -55%;
the uranium-containing hydrofluoric acid solution has a uranium concentration range of 40-120 mg/L.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
in step II, the stirring is mechanical stirring.
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| US4234555A (en) * | 1978-06-29 | 1980-11-18 | The United States Of America As Represented By The United States Department Of Energy | Removal of uranium from aqueous HF solutions |
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| CN110330164A (en) * | 2019-08-14 | 2019-10-15 | 盛隆资源再生（无锡）有限公司 | A kind of method of alkalinity high fluorine Sewage treatment fluorine resource and sodium resource with high salt |
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| US4234555A (en) * | 1978-06-29 | 1980-11-18 | The United States Of America As Represented By The United States Department Of Energy | Removal of uranium from aqueous HF solutions |
| CN1075338A (en) * | 1992-02-11 | 1993-08-18 | 皮奇尼铀公司 | The method of recovery and purification of high-concentration uranium-based alloy |
| TW201043573A (en) * | 2009-06-10 | 2010-12-16 | Inst Nuclear Energy Res | Method for separating and recycling uranium and fluorine from solution |
| CN102633347A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for treating cadmium-containing wastewater by utilizing microwave modified ardealite |
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