CN114558606A - Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof - Google Patents
Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof Download PDFInfo
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- CN114558606A CN114558606A CN202210191719.2A CN202210191719A CN114558606A CN 114558606 A CN114558606 A CN 114558606A CN 202210191719 A CN202210191719 A CN 202210191719A CN 114558606 A CN114558606 A CN 114558606A
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- seawater
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- containing wastewater
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 128
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 239000013535 sea water Substances 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 29
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940116357 potassium thiocyanate Drugs 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000005289 uranyl group Chemical group 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- 238000005286 illumination Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B01J35/19—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of new energy development, and discloses a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof, wherein the catalyst is prepared by the following steps: grinding and uniformly mixing carbon nitride, potassium chloride and potassium thiocyanate, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor; washing the catalyst precursor with clear water and an alcohol solution in sequence to wash off salt and impurities on the surface of the catalyst precursor, and obtaining a washed catalyst precursor; and (3) freeze-drying the catalyst precursor to obtain the catalyst. The catalyst has good cycle performance, uranium can be continuously separated from a water body by using the separation method, only sunlight is needed in the whole process, and the method is green, environment-friendly, sustainable and pollution-free.
Description
Technical Field
The invention relates to the technical field of new energy development, in particular to a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof.
Background
The development and utilization of uranium resources have important significance on the sustainable development of nuclear energy. However, limited resources of terrestrial uranium ores have been explored. About 45 million tons of uranium are contained in seawater worldwide, which is thousands times of the known terrestrial uranium resources. At present, the widely researched method for extracting uranium from seawater is mainly an adsorption method, but the method has the defects of poor selectivity, low extraction efficiency, difficult elution and high cost. The photocatalysis method proposed in recent years provides a new idea for separating and extracting uranium in water. The photocatalysis method has the advantages of greenness, high efficiency, high selectivity, large extraction capacity and the like, and has wide application prospect. However, in practical applications, the photocatalytic method can only occur under illumination, the photocatalytic reduction of uranium cannot be performed when no illumination is provided at night, and the uranium reduction product is easily oxidized and dissolved again, which affects the photocatalytic reduction efficiency.
To sum up, the problem that current photocatalysis uranium extraction technology exists is: the existing uranium photocatalytic reduction technology can only be carried out under the drive of illumination, the catalytic reduction of uranium cannot be continuously carried out in the night, and the oxidation and the redissolution of extracted uranium are easily caused. In summary, it is difficult to realize continuous photocatalytic reduction of uranium under light and dark conditions in the prior art, so as to achieve the purpose of extracting uranium from seawater day and night.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof.
The catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and the application thereof are realized by the following technical scheme:
the first purpose of the invention is to provide a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
grinding and uniformly mixing carbon nitride, potassium chloride and potassium thiocyanate, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor;
washing the catalyst precursor with water and an alcohol solution in sequence to wash off salt and impurities on the surface of the catalyst precursor, thereby obtaining a washed catalyst precursor;
and (3) freeze-drying the washed catalyst precursor to obtain the catalyst.
Further, the mass ratio of the carbon nitride to the potassium chloride to the potassium thiocyanate is 1: 1-3: 4-6.
Further, the vacuum degree of the freeze drying treatment is below 10Pa, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
Further, the temperature is raised from room temperature to 500-600 ℃ at a rate of 5-10 ℃/min.
Further, washing the catalyst precursor by water until no potassium ion is detected in the washing liquid; the catalyst precursor is then washed with anhydrous ethanol to remove alcohol-soluble impurities in the catalyst precursor.
The second purpose of the invention is to provide an application of the catalyst based on any one of the above in extraction and separation of uranium in uranium-containing wastewater or seawater.
Further, separating uranium from uranium-containing wastewater or seawater by the following steps:
uniformly dispersing the catalyst in an aqueous solvent, then adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, adjusting the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a first mixed solution, irradiating the first mixed solution under a xenon lamp for 8-60 min under the atmosphere of nitrogen, carrying out suction filtration to separate a solid-liquid phase, and collecting a solid to obtain a uranium-containing extract;
or uniformly dispersing the catalyst material in a water solvent, adjusting the pH value to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a second mixed solution, irradiating the second mixed solution under the atmosphere of nitrogen under natural light or a xenon lamp until the color of the second mixed solution is changed from yellow to blue, forming stable reductive free radicals on the surface of the material, removing a light source, adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, reacting for 40 minutes, filtering to separate a solid-liquid phase and collecting a solid, thereby obtaining a uranium-containing extract;
and 2, separating and extracting uranium:
and oxidizing the uranium-containing extract in the air for 8-16 h, adding a dilute nitric acid solution, uniformly stirring to elute uranium, filtering, and collecting filtrate to obtain a solution enriched in uranyl.
Further, the ratio of the total volume of the hydrosolvent and the uranium-containing wastewater or uranium-containing seawater to the amount of the catalyst is 1mL: 0.5-1.5 mg.
Further, the sacrificial agent is any one of methanol, ethanol, isopropanol and formic acid.
Further, the dosage ratio of the sacrificial agent to the catalyst is 1mL: 4-8 mg.
Further, the blowing-in speed of the nitrogen is 120mL/min, and the blowing-in time is 1-3 h.
Further, the dosage ratio of the dilute nitric acid solution to the catalyst is 1mL: 5-10 mg;
the concentration of the dilute nitric acid solution is 0.05-0.15 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, carbon nitride powder, potassium chloride and potassium thiocyanate are uniformly mixed and sintered to obtain a catalyst precursor, and the catalyst precursor is sequentially cleaned by water and an alcohol solution to remove redundant salt and alcohol-soluble impurities in the catalyst precursor, so that the influence of the salt and the alcohol-soluble impurities on the performance of the catalyst is avoided. The catalyst is obtained by freeze-drying the washed catalyst precursor.
The catalyst can effectively carry out photocatalytic reduction on the hexavalent uranium in the uranium-containing wastewater or uranium-containing seawater under illumination; the catalyst of the invention generates charge separation on the surface of the catalyst under illumination to form stable and long-acting reductive free radicals, N2Under protection, the free radical can stably exist for more than 48 hours; and the catalyst of the invention can sustain through the free radical in the absence of lightHexavalent uranium in the reduction solution can be reduced, and tetravalent uranium generated by reduction on the surface of the catalyst can be prevented from being oxidized and dissolved, so that the catalyst can achieve the effect of extracting uranium from seawater in day and night.
According to the invention, the catalyst is used for treating the uranium-containing wastewater or uranium-containing seawater, so that hexavalent uranium in the uranium-containing wastewater or uranium-containing seawater can be quickly reduced on the surface of the catalyst, the reduced uranium on the surface of the catalyst is separated into a dilute nitric acid solution through dilute nitric acid treatment, and then the catalyst is filtered out, so that the uranium in the uranium-containing wastewater or uranium-containing seawater is extracted into the dilute nitric acid solution, and the extraction and separation of the uranium in the uranium-containing wastewater or uranium-containing seawater are realized.
The catalyst has good cycle performance, uranium can be continuously separated from a water body by using the separation method, only sunlight is needed in the whole process, and the method is green, environment-friendly, sustainable and pollution-free.
Drawings
FIG. 1 is a schematic diagram of a uranium separation route according to the present invention;
FIG. 2 is an XPS spectrum of the catalyst of example 1 of the present invention;
FIG. 3 is an IR spectrum of the catalyst of example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of the catalyst in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a catalyst in example 1 of the present invention;
FIG. 6 is a transmission electron micrograph of a catalyst in example 1 of the present invention;
FIG. 7 is a UV-visible diffuse reflectance plot of the catalyst of example 1 of the present invention;
FIG. 8 is a photocurrent response of the catalyst of example 1 of the present invention;
FIG. 9 shows that the surface free radical signal of the catalyst of example 2 of the present invention can be kept stable within 48 hours;
FIG. 10 is an XPS spectrum of reduced uranium after the catalyst has been exposed to light for various periods of time in example 2 of the present invention;
FIG. 11 shows the effect of the catalyst of example 1 of the present invention on uranium photocatalysis under light;
fig. 12 shows the dark catalytic effect on uranium of the catalyst after illumination in example 2 of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
In the present invention, the concentration is 4.0X 10-3mol/L UO2(NO3)2The solution was used as uranium-containing wastewater or uranium-containing seawater, and the following operations were carried out in examples.
Example 1
The embodiment provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
respectively weighing carbon nitride, potassium thiocyanate and potassium chloride in corresponding mass ratio of 1:2:6, grinding and uniformly mixing, placing in a quartz boat, placing in a tube furnace, heating to 550 ℃ at the speed of 8 ℃/min, and preserving heat for 4h to obtain a faint yellow solid catalyst precursor;
then grinding the catalyst precursor into powder, and washing the ground catalyst precursor for a plurality of times by using ultrapure water until K can not be detected in the washing liquid after washing+Subsequently, washing the ground catalyst precursor for several times by using absolute ethyl alcohol to wash off alcohol-soluble impurities in the catalyst precursor, thereby reducing the influence of other substances on the catalytic performance of the catalyst and improving the catalytic performance of the catalyst; the catalyst powder was then freeze-dried at-15 ℃ under 10Pa for 12 hours to remove water, thereby obtaining a catalyst.
Example 2
The embodiment provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
respectively weighing carbon nitride, potassium thiocyanate and potassium chloride with corresponding mass according to the mass ratio of 1:3:5, grinding and uniformly mixing the materials, putting the materials into a quartz boat, putting the quartz boat into a tubular furnace, heating the quartz boat to 550 ℃ at the speed of 8 ℃/min, and preserving the temperature for 4 hours to obtain a faint yellow solid catalyst precursor;
then grinding the catalyst precursor into powder, washing the ground catalyst precursor for a plurality of times by using ultrapure water until K cannot be detected in the washing liquid after washing+Subsequently, washing the ground catalyst precursor for several times by using absolute ethyl alcohol to wash off alcohol-soluble impurities in the catalyst precursor, thereby reducing the influence of other substances on the catalytic performance of the catalyst and improving the catalytic performance of the catalyst; the catalyst powder was then freeze-dried at-10 ℃ under 8Pa for 10 hours to remove water, thereby obtaining a catalyst.
Example 3
This example differs from example 1 in that:
in this example, the mass ratio of carbon nitride, potassium chloride and potassium thiocyanate was 1:1: 4.
In this example, the temperature was maintained at 500 ℃ for 5 hours at a rate of 5 ℃/min.
In the embodiment, the vacuum degree of freeze drying treatment is below 10Pa, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
Example 4
This example differs from example 1 in that:
in this example, the mass ratio of carbon nitride, potassium chloride and potassium thiocyanate was 1:3: 6.
In this example, the temperature was 600 ℃, the holding time was 3 hours, and the temperature rise rate was 10 ℃/min.
In the embodiment, the vacuum degree of the freeze drying treatment is less than 10Pa, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
Example 5
This example provides a separation method for extracting and separating uranium from uranium-bearing wastewater or seawater, and uses the catalyst of example 1 to carry out the separation method for uranium with concentration of 4.0 × 10-3mol/L UO2(NO3)2Uranium in the solution is separated and extracted, and the method comprises the following specific steps:
15mg of the catalyst material was weighed into a quartz tube and dispersed by sonication uniformly in 14.625mL of distilled water, followed by the addition of 0.375mL4.0×10-3mol/L UO2(NO3)2The solution was mixed well, pH adjusted to 6.0, 2.5mL methanol was added as sacrificial agent, and N was bubbled through 120 g in the dark2Removing dissolved oxygen for 2 hr, irradiating under 500W xenon lamp (with 420nm filter) for 40min, and filtering to obtain uranium-containing extract. Oxidizing the obtained uranium-containing extract in air for 12h, adding 2mL0.1mol/L dilute nitric acid solution, stirring for 10min, and filtering to obtain UO2(NO3)2And transferring the uranium in the solution to filtrate to realize uranium separation.
Example 6
This example provides a separation method for extracting and separating uranium from uranium-bearing wastewater or seawater, and the catalyst of example 2 is used in this example to carry out the separation of uranium with a concentration of 4.0 × 10-3mol/L UO2(NO3)2Uranium in the solution is separated and extracted, and the method comprises the following specific steps:
15mg of the catalyst material was weighed into a quartz tube and dispersed by sonication evenly in 14.625mL of distilled water, the pH was adjusted to 6.0, 2.5mL of methanol was added as a sacrificial agent, and N was bubbled at 120mL/min2Bubbling for 2 hours to remove dissolved oxygen, then placing under 500W xenon lamp (adding 420nm filter) for 1min, after the solution color changes from light yellow to blue, adding 0.375mL of 4.0 × 10-3mol/L UO2(NO3)2The solution is mixed evenly, reacted for 40min and filtered to obtain the uranium-containing extract. Oxidizing the obtained uranium-containing extract in air for 12h, adding 2mL0.1mol/L dilute nitric acid solution, stirring for 10min, and filtering to obtain UO2(NO3)2Transferring the uranium in the solution to the filtrate to realize the separation of the uranium.
Example 7
This example differs from example 5 in that, when the performance test on the catalyst was carried out:
adjusting the pH value to 5.5;
the xenon lamp irradiation time is 8 min;
the oxidation time of the uranium-containing extract is 8 h;
the ratio of the total volume of the hydrosolvent and the uranium-containing wastewater or uranium-containing seawater to the amount of the catalyst is 1mL to 0.5 mg.
The sacrificial agent is ethanol, and the dosage ratio of the sacrificial agent to the catalyst is 1mL to 4 mg.
The nitrogen bubbling time was 1 h.
The dosage ratio of the dilute nitric acid solution to the catalyst is 1mL:5mg, and the concentration of the dilute nitric acid solution is 0.05 mol/L.
Example 8
This example differs from example 5 in that, when the performance test on the catalyst was carried out:
adjusting the pH value to 6.5;
the xenon lamp irradiation time is 60 min;
the oxidation time of the uranium-containing extract is 16 h;
the ratio of the total volume of the hydrosolvent and the uranium-containing wastewater or uranium-containing seawater to the amount of the catalyst is 1mL:1.5 mg.
The sacrificial agent is isopropanol, and the dosage ratio of the sacrificial agent to the catalyst is 1mL to 8 mg.
The nitrogen bubbling time was 3 h.
The dosage ratio of the dilute nitric acid solution to the catalyst is 1mL:10mg, and the concentration of the dilute nitric acid solution is 0.15 mol/L.
Example 9
This example differs from example 6 in that, when the performance test for the catalyst was performed:
adjusting the pH value to 6.5;
addition of UO2(NO3)2The reaction time after the solution is 30 min;
the sacrificial agent is formic acid.
Test section
In order to verify the performance of the catalysts prepared according to the invention, the following tests were carried out:
(one) XPS test
The catalyst of example 1 was used in the present invention, and the results of XPS test are shown in fig. 2, which shows that the catalyst material prepared by the method of the present invention has obvious potassium element (K)+) And XPS characteristic peak of cyano group (-C.ident.N), indicating thatPotassium ions and cyano groups were successfully doped into the catalyst.
(II) Infrared Spectroscopy
The catalyst of example 1 was subjected to IR spectroscopy and the results are shown in FIG. 3. it can be seen that the catalyst material prepared by the process of the present invention has an IR vibration peak similar to that of graphite-phase carbon nitride, which is between 3000 and 3300cm-1The characteristic peak between corresponds to the stretching vibration of N-H and O-H bonds; is positioned at 1000--1The characteristic peak between the two corresponds to the stretching vibration of the aromatic C-N heterocyclic skeleton in the heptazine ring; 810cm-1The characteristic peak at (a) corresponds to the stretching vibration of the triazinyl ring. In addition, at 2170cm-1A strong infrared vibration peak appears, which corresponds to the asymmetric stretching vibration peak of the cyano group, and the result further confirms the successful doping of the cyano group.
(III) X-ray diffraction test
The catalyst of example 1 is taken as an example, and an X-ray diffraction test is carried out on the catalyst, and the result is shown in figure 4, so that the catalyst material prepared by the method has a relatively obvious signal peak at the position with a diffraction angle of 27.9 degrees, and corresponds to a (002) crystal face stacked between layers of graphite-phase carbon nitride; this diffraction angle was slightly shifted to a high angle compared to the (002) crystal plane diffraction angle (27.5 °) of the classical graphite phase carbon nitride, indicating that the catalyst material prepared had a smaller stacking distance between the layers of the classical graphite phase carbon nitride material. In addition, diffraction peaks appearing at 8.0 and 9.9 ° can be assigned to the (110) and (010) crystal planes of the polyimide structure.
(IV) topography testing
The catalyst of example 1 was used as an example of the present invention, and the results of the scanning electron microscope test and the transmission electron microscope test were shown in fig. 5 and 6, respectively. As can be seen from fig. 5, the catalyst material prepared by the method of the present invention exhibits irregular fragments and a layered packing structure; and as can be seen from fig. 6, the catalyst material prepared by the method of the present invention exhibits irregular lamellar nanosheet stacking, and the nanosheets are smaller in size.
(V) diffuse UV-visible reflectance
The catalyst of example 1 is taken as an example, and an ultraviolet-visible diffuse reflection test is performed on the catalyst, and the result is shown in fig. 7, which shows that the catalyst material prepared by the method of the invention has higher light absorption in both ultraviolet and visible light regions.
(VI) photocurrent response
The catalyst of example 1 is taken as an example, a photocurrent response test is performed on the catalyst, and the result is shown in fig. 8, which shows that when the catalyst is irradiated by light, a photocurrent signal of the catalyst material is rapidly increased, which indicates that the catalyst material prepared by the method of the present invention has a relatively obvious photocurrent response, and indicates that the catalyst material has a high-efficiency photo-generated carrier separation capability.
(VII) free radical stability test
In order to ensure that the catalyst prepared by the method can be used as a catalyst in the process of extracting and separating uranium from uranium-containing wastewater or seawater, the catalyst of example 2 is taken as an example, the stability of free radicals of the catalyst is tested, and the result is shown in fig. 9, so that the catalyst of example 2 can still keep stable in 48 hours, which shows that the catalyst prepared by the method of the invention has good stability and can be used as a catalyst in the process of extracting and separating uranium from uranium-containing wastewater or seawater.
In order to further verify the separation effect of the catalyst prepared by the method in the process of extracting and separating uranium from uranium-containing wastewater or seawater, the following tests are carried out:
the catalyst in the embodiment 2 is irradiated for 10 minutes by a 500W xenon lamp, placed in the dark for different time, added with uranyl solution, analyzed for change of uranium valence state by XPS, and reduced to mainly generate non-stoichiometric uranium dioxide (UO)2+x) As shown in FIG. 10, it can be seen that the free radicals formed after the irradiation of light can maintain good reactivity within 24 hours, and uranium in the solution is used as UO2+xThe form is completely deposited on the surface of the catalyst. After the catalyst is placed for 48 hours after illumination, part of uranium is adsorbed in the form of uranyl, but part of uranium is reduced to quadrivalence, which shows that free radicals formed on the surface of the catalyst after illumination can exist stably for a long time, and at leastThe uranium in the solution can be completely reduced and deposited within 24 hours.
The present invention takes 1mL of each suspension of example 5 and example 6 at different reaction stages, filters the suspension, and measures the concentration in the supernatant by azoarsine III spectrophotometry, and the results are shown in FIGS. 11 and 12.
As can be seen from fig. 11, after the catalyst of example 1 is mixed with a uranium-containing solution, the mixture is reacted for 2 hours in the dark, and an adsorption equilibrium is reached, at this time, about 75% of the uranium in the solution is adsorbed on the catalyst, at this time, a 500W xenon lamp is used for irradiating a catalytic system, and the photocatalytic reaction makes all the uranium completely reduced within 5 minutes, deposited on the surface of the catalyst and extracted.
As can be seen from fig. 12, after the catalyst of example 2 was irradiated with a 500W xenon lamp for 10 minutes, and mixed with a uranium-containing solution, under the protection of nitrogen, uranium in the solution was completely reduced within 5 minutes, deposited on the surface of the catalyst and extracted, and the extraction rate was 100%.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A catalyst for extracting and separating uranium from uranium-containing wastewater or seawater is characterized by being prepared by the following steps:
grinding and uniformly mixing carbon nitride, potassium chloride and potassium thiocyanate, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor;
washing the catalyst precursor with water and an alcohol solution in sequence to obtain a washed catalyst precursor;
and (3) freeze-drying the washed catalyst precursor to obtain the catalyst.
2. The catalyst according to claim 1, wherein the mass ratio of the carbon nitride to the potassium chloride to the potassium thiocyanate is 1:1 to 3:4 to 6.
3. The catalyst according to claim 1, wherein the degree of vacuum of the freeze-drying treatment is 10Pa or less, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
4. The catalyst of claim 1, wherein the temperature is raised from room temperature to 500-600 ℃ at a rate of 5-10 ℃/min.
5. Use of a catalyst according to any one of claims 1 to 4 for the extractive separation of uranium from uranium-bearing waste water or seawater.
6. Use according to claim 5, wherein uranium is separated from uranium-containing waste water or seawater by:
step 1, catalytic reduction:
uniformly dispersing the catalyst in an aqueous solvent, then adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, adjusting the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a first mixed solution, irradiating the first mixed solution under a nitrogen atmosphere and a xenon lamp for 8-60 min, performing solid-liquid separation, and collecting separated solids to obtain a uranium-containing extract;
or uniformly dispersing the catalyst material in a water solvent, adjusting the pH value to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a second mixed solution, irradiating the second mixed solution under the atmosphere of nitrogen and natural light or a xenon lamp until the color of the second mixed solution changes from yellow to blue, forming stable reductive free radicals on the surface of the material, removing a light source, adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, reacting for 30-60 min, performing solid-liquid separation, and collecting separated solids to obtain a uranium-containing extract;
and 2, separating and extracting uranium:
and oxidizing the uranium-containing extract in the air for 8-16 h, adding a dilute nitric acid solution, uniformly stirring to elute uranium, filtering, and collecting filtrate to obtain a solution enriched in uranyl.
7. The use of claim 6, wherein the sacrificial agent is any one of methanol, ethanol, isopropanol, and formic acid.
8. The application of claim 6, wherein the ratio of the total volume of the water solvent and the uranium-containing wastewater or the uranium-containing seawater to the amount of the catalyst is 1mL: 0.5-1.5 mg;
the dosage ratio of the sacrificial agent to the catalyst is 1mL: 4-8 mg.
9. The use according to claim 6, wherein the nitrogen gas is bubbled at a rate of 120mL/min for a period of 1-3 hours.
10. The use of claim 6, wherein the dosage ratio of the dilute nitric acid solution to the catalyst is 1mL: 5-10 mg;
the concentration of the dilute nitric acid solution is 0.05-0.15 mol/L.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115148389A (en) * | 2022-07-01 | 2022-10-04 | 华北电力大学 | Photocatalytic uranium removal method without catalyst |
CN115821080A (en) * | 2022-10-17 | 2023-03-21 | 西北工业大学 | Process for extracting uranium from uranium-containing wastewater and preparing yellow cake |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2634731A1 (en) * | 1975-08-04 | 1977-02-17 | Ciba Geigy Ag | Metal carbide-nitride powder prodn. - using triazine or pyrimidine cpd. as carbon and nitrogen source |
US20120175316A1 (en) * | 2009-07-17 | 2012-07-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for extracting at least one chemical element from a molten salt medium |
CN107486231A (en) * | 2017-08-24 | 2017-12-19 | 福州大学 | A kind of preparation method of graphite phase carbon nitride colloid photochemical catalyst |
CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
CN108906102A (en) * | 2018-06-11 | 2018-11-30 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | A method of uranium extraction is carried out using photocatalysis technology under visible light |
CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
CN111018041A (en) * | 2019-12-19 | 2020-04-17 | 南华大学 | Preparation method and application of polypyrrole graphite phase carbon nitride composite material for treating uranium-containing wastewater through photocatalytic reduction |
CN111627588A (en) * | 2020-06-15 | 2020-09-04 | 华北电力大学 | Application of graphene aerogel in removing uranium through photocatalysis |
CN111792628A (en) * | 2020-07-07 | 2020-10-20 | 清华大学 | Double-function carbon nitride material synthesized by molten salt method and preparation method and application thereof |
CN113171766A (en) * | 2021-04-29 | 2021-07-27 | 常州大学 | Preparation method and application of oil absorption/adsorption metal ion/photocatalysis integrated magnetic nano graphite phase carbon nitride material |
CN113499790A (en) * | 2021-07-08 | 2021-10-15 | 西南科技大学 | Preparation and application of Ag-doped CdSe nanosheet photocatalytic material separated by uranium reduction |
-
2022
- 2022-02-28 CN CN202210191719.2A patent/CN114558606B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2634731A1 (en) * | 1975-08-04 | 1977-02-17 | Ciba Geigy Ag | Metal carbide-nitride powder prodn. - using triazine or pyrimidine cpd. as carbon and nitrogen source |
US20120175316A1 (en) * | 2009-07-17 | 2012-07-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for extracting at least one chemical element from a molten salt medium |
CN107486231A (en) * | 2017-08-24 | 2017-12-19 | 福州大学 | A kind of preparation method of graphite phase carbon nitride colloid photochemical catalyst |
CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
CN108906102A (en) * | 2018-06-11 | 2018-11-30 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | A method of uranium extraction is carried out using photocatalysis technology under visible light |
CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
CN111018041A (en) * | 2019-12-19 | 2020-04-17 | 南华大学 | Preparation method and application of polypyrrole graphite phase carbon nitride composite material for treating uranium-containing wastewater through photocatalytic reduction |
CN111627588A (en) * | 2020-06-15 | 2020-09-04 | 华北电力大学 | Application of graphene aerogel in removing uranium through photocatalysis |
CN111792628A (en) * | 2020-07-07 | 2020-10-20 | 清华大学 | Double-function carbon nitride material synthesized by molten salt method and preparation method and application thereof |
CN113171766A (en) * | 2021-04-29 | 2021-07-27 | 常州大学 | Preparation method and application of oil absorption/adsorption metal ion/photocatalysis integrated magnetic nano graphite phase carbon nitride material |
CN113499790A (en) * | 2021-07-08 | 2021-10-15 | 西南科技大学 | Preparation and application of Ag-doped CdSe nanosheet photocatalytic material separated by uranium reduction |
Non-Patent Citations (3)
Title |
---|
HUIHUI GAO ET.AL: "Metal organic framework derived heteroatoms and cyano (-C≡N) group co-decorated porous g-C3N4 nanosheets for improved photocatalytic H2 evolution and uranium(VI) reduction", vol. 570, pages 2 * |
PING DENG ET.AL: "One-step preparation of novel K+ and cyano-group co-doped crystalline polymeric carbon nitride with highly efficient H2 evolution", vol. 601, pages 2 * |
任金秋;司明强;张灵杰;张晶晶;陆春海;: "光催化及其处理铀废水的研究进展", no. 02, pages 62 - 66 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115148389A (en) * | 2022-07-01 | 2022-10-04 | 华北电力大学 | Photocatalytic uranium removal method without catalyst |
CN115821080A (en) * | 2022-10-17 | 2023-03-21 | 西北工业大学 | Process for extracting uranium from uranium-containing wastewater and preparing yellow cake |
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