CN109972173B - Device for recycling uranium in nuclear wastewater by using solar-based modified NZVI three-dimensional electrochemical method - Google Patents
Device for recycling uranium in nuclear wastewater by using solar-based modified NZVI three-dimensional electrochemical method Download PDFInfo
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- CN109972173B CN109972173B CN201910382389.3A CN201910382389A CN109972173B CN 109972173 B CN109972173 B CN 109972173B CN 201910382389 A CN201910382389 A CN 201910382389A CN 109972173 B CN109972173 B CN 109972173B
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 68
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002351 wastewater Substances 0.000 title claims abstract description 57
- 238000002848 electrochemical method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 58
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 55
- 238000001556 precipitation Methods 0.000 claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005485 electric heating Methods 0.000 claims description 14
- 239000002918 waste heat Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000003311 flocculating effect Effects 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- 239000011358 absorbing material Substances 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 12
- 238000005189 flocculation Methods 0.000 abstract description 6
- 230000016615 flocculation Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000008247 solid mixture Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a device for recycling uranium in nuclear wastewater by a modified NZVI three-dimensional electrochemical method based on solar energy, which comprises a wastewater PH regulating tank, a three-dimensional electrolysis device, an automatic feeder and a precipitation waste thermal evaporation tank connected with the bottom of the electrolysis device. The three-dimensional electrolytic device takes modified NZVI as a particle electrode, inert graphite as an anode, an iron flocculation polar plate as a cathode, U (VI) in nuclear wastewater is reduced into U (IV) and precipitated through electrolytic reaction, and a solid mixture of uranium is obtained after the precipitation mixed solution is heated and evaporated through solar energy. The modified NZVI provided by the invention is a novel composite material, is nontoxic and harmless, and can effectively solve the problem that secondary environmental pollution is easy to generate in the nuclear wastewater treatment process. The power consumption required by the device can be all derived from solar energy, the whole-process intelligent operation can be realized, and the device can also be expanded into a plurality of devices which work simultaneously, so that the working efficiency is greatly improved.
Description
Technical Field
The invention relates to application of solar energy and composite material research in the field of electrochemical method treatment of nuclear wastewater, in particular to a device for recycling uranium in nuclear wastewater by a modified NZVI three-dimensional electrochemical method based on solar energy.
Background
The waste water with natural radionuclide uranium can be generated in the uranium ore mining and smelting process and the nuclear facility operation process, and the waste water has serious harm to the ecological environment. The valences of the radionuclide uranium which can exist stably are hexavalent uranium U (VI) and tetravalent uranium U (IV), wherein U (IV) is insoluble in water and mainly adopts solid asphaltic uranium ore UO 2 Exists in a form; u (VI) is in the form of UO in solution 2 2+ Is easy to dissolve and migrate in water environment. The water body uranium removal mainly refers to removal of hexavalent uranium U (VI) and compounds thereof, so that a restoration technology based on reduction of hexavalent uranium is a research hot spot for treating nuclear wastewater uranium pollution. The high-efficiency and low-cost treatment of uranium-containing wastewater is not realized at present, and the uranium-containing wastewater treatment technology with wide applicability, low operation cost and environmental protection is still to be further developed and researched.
Therefore, the invention aims to provide a nuclear wastewater treatment method with low cost and high efficiency, and the method has the advantages of wide applicability, low running cost and environmental protection in a solar energy enrichment area.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a device for recycling uranium in nuclear wastewater by a modified NZVI three-dimensional electrochemical method based on solar energy.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the device comprises a wastewater PH regulating tank, an electrolysis device connected with the wastewater PH regulating tank, an automatic feeder connected with the top of the electrolysis device and a precipitation waste thermal evaporation tank connected with the bottom of the electrolysis device, wherein the electrolysis device comprises an electrolysis tank, an electrolysis cathode and an electrolysis anode are arranged in the electrolysis tank, the electrolysis cathode and the electrolysis anode are connected with a power supply, the bottom of the electrolysis tank is in a funnel shape, the bottom of the electrolysis tank is connected with the precipitation waste thermal evaporation tank through a precipitation waste outlet pipe, and the top of the electrolysis tank is connected with a supernatant fluid delivery pipe;
the waste water PH regulating tank is provided with a waste liquid inlet pipe and a waste liquid outlet pipe, and the waste liquid outlet pipe is positioned at the bottom of the waste water PH regulating tank and is communicated with the electrolytic tank;
the automatic feeder comprises a modified NZVI powder feeding box, wherein the modified NZVI powder feeding box is connected with a funnel pipe through a modified NZVI powder feeding pipe, and the bottom of the funnel pipe is connected with an electrolytic cell.
The modified NZVI powder charging box is put into the electrolytic cell, and is used as a particle electrode, and respectively forms a three-dimensional electrode system with an electrolytic cathode and an electrolytic anode in the electrolytic cell. The iron ions are converted into ferroferric oxide through electrolytic reaction, hexavalent uranium U (VI) in the nuclear waste liquid is reduced into tetravalent uranium U (IV), and the tetravalent uranium U (IV) and the ferroferric oxide are subjected to condensation coprecipitation.
Wherein the nuclear wastewater is introduced into a wastewater PH adjusting tank through a waste liquid inlet pipe and HNO is used 3 Or NaOH adjusts the ph=5 of the solution, modified NZVI powder feed box stores modified NZVI material (coated NZVI/high-gluten powder).
According to the device for recycling uranium in nuclear wastewater by using the solar-energy-based modified NZVI three-dimensional electrochemical method, the electrolytic anode is made of inert graphite, and the electrolytic cathode is an iron flocculating electrode.
According to the device for recycling uranium in nuclear wastewater by using the modified NZVI three-dimensional electrochemical method based on solar energy, the electric heating device is arranged at the bottom of the precipitation waste heat evaporation tank, the solar concentrating mirror is arranged on one side of the precipitation waste heat evaporation tank and is in a hemispherical shape and fixed on the support, the spherical surface faces the sun in the south, and the reflected light of the solar concentrating mirror is focused on the surface of the precipitation waste heat evaporation tank.
According to the device for recycling uranium in nuclear wastewater by using the solar-energy-based modified NZVI three-dimensional electrochemical method, the surface of the precipitation waste thermal evaporation tank is coated with the black coating, and the black coating is made of a heat absorbing material.
According to the device for recycling uranium in nuclear wastewater by using the solar-based modified NZVI three-dimensional electrochemical method, the low-frequency stirrer is arranged in the electrolytic cell, and the low-frequency stirrer is connected with a power supply.
According to the device for recycling uranium in nuclear wastewater by the modified NZVI three-dimensional electrochemical method based on solar energy, the PH regulating tank and the electrolytic tank for wastewater are arranged on the base, the solar cell panel is arranged on the base, and the solar cell panel is connected with the automatic control module.
According to the device for recycling uranium in nuclear wastewater by using the modified NZVI three-dimensional electrochemical method based on solar energy, the waste liquid outlet pipe, the supernatant liquid delivery pipe, the modified NZVI powder supply pipe and the precipitation waste outlet pipe are provided with control valves.
The device for recycling uranium in the nuclear wastewater by the modified NZVI three-dimensional electrochemical method based on solar energy comprises a storage battery connected with a solar cell panel, a solar controller connected with the storage battery and a valve controller.
The device for recycling uranium in nuclear wastewater by the modified NZVI three-dimensional electrochemical method based on solar energy is characterized in that the model of a solar controller is SR602, and the storage battery is connected with an electrolytic cathode, an electrolytic anode, an electric heating device and a low-frequency stirrer;
the model of the valve controller is DATA-6321, and the valve controller is connected with the control valve on the waste liquid outlet pipe, the supernatant liquid outlet pipe, the modified NZVI powder supply pipe and the precipitation waste outlet pipe.
The device for recycling uranium in nuclear wastewater by using the solar-based modified NZVI three-dimensional electrochemical method is characterized in that the electric heating device is an electric heating wire which is arranged at the bottom of a precipitation waste thermal evaporation tank in an annular mode.
The corresponding operation steps of the device are as follows: (1) The high-gluten powder is used as a carrier, and a liquid phase reduction method is adopted to prepare the coated NZVI/high-gluten powder. (2) The modified NZVI material (coated NZVI/high-strength powder) is used as a particle electrode, inert graphite is used as an anode, and an iron flocculation polar plate is used as a cathode to build a three-dimensional electrolytic cell. (3) The solar panel is used as a photovoltaic conversion device to provide required electric power for the three-dimensional electrochemical device. (4) The drum coated with black heat absorbing material is used as a precipitation waste treatment tank, the solar concentrating mirror is used as a photo-thermal conversion device to thermally evaporate precipitation waste, and the obtained solid substance is uranium mixture. (5) After the electrolytic reaction for 60min, the residual uranium content in the supernatant of the three-dimensional electrolytic cell is lower than the national safety discharge standard, and the uranium can be used as the standard water for safety discharge.
The modified NZVI composite material is used as a particle electrode of a three-dimensional electrochemical device, and has the advantages of small particle size, good dispersibility and large reaction surface area. The preparation process comprises the following steps: accurately measuring 15mL of ethanol, and adding 35mL of water to obtain 30% absolute ethanol; 50mL of 30% absolute ethanol was weighed into a conical flask, and 4.83g of FeCl was weighed 3 Placing 6H2O in a conical flask, mixing with 30% absolute ethanol, and stirring to obtain FeCl 3 A solution; weighing 20 g of common high-gluten powder, grinding for 15min by using a ball mill, and sieving by a 100-mesh sieve to obtain a high-gluten powder raw material. Accurately weighing 2g of high-gluten powder raw material and adding the high-gluten powder raw material into FeCl 3 Stirring the solution for 1h on a magnetic stirrer; 4.32g KBH4 was weighed into 100mL H2O to make a 0.8mol/L KBH4 solution and FeCl was slowly added 3 Continuously stirring the solution in a solution conical flask along with black foam during adding, and stirring for 30min to obtain a nano zero-valent iron solution coated on high-strength powder; separation of nano zero-valent iron solution with deionized water and absolute ethyl alcoholAnd (3) washing for 3 times, and drying in a vacuum drying oven at 65 ℃ to obtain coated NZVI/high-gluten powder.
The modified NZVI is used as a particle electrode, and the particle electrode, the graphite inert electrode and the iron flocculation electrode form a three-dimensional electrode system. Inert graphite is used as an anode, and an iron flocculating electrode is used as a cathode. The iron ions are converted into ferroferric oxide through electrolytic reduction reaction, hexavalent uranium U (VI) in the nuclear waste liquid is reduced into tetravalent uranium U (IV), and the tetravalent uranium U (IV) and the ferroferric oxide are subjected to condensation coprecipitation. The power consumption required by the electrochemical device is powered by a solar-charged storage battery;
an automatic feeder is arranged for feeding the modified NZVI powder at fixed time and fixed quantity. The time and weight of the feed are set by the valve controller. The low-frequency stirrer is arranged above the electrolysis device, the rotation frequency is lower than 10 revolutions per second, and the electrolytic reaction and the coagulation and precipitation process can be accelerated. The required power consumption is powered by a solar charged battery.
The solar panel adopts the 140W amorphous silicon solar panel, and in a solar energy enrichment area, the generated power can meet the electric energy requirement of an electrolysis and automatic control circuit. The automatic control module is divided into an electrolysis circuit, an automatic feeder control circuit, a low-frequency stirrer control circuit and a solar automatic tracking device. The automatic control module power consumption is supplied by a solar charging storage battery, and the automatic control module and the solar panel are arranged on the same bracket.
The precipitation waste heat evaporation tank is a barrel with the diameter of 0.5 m and the height of 1 m, the outer surface of the barrel is coated with black heat absorption paint, and the black paint of the barrel strongly absorbs reflected sunlight and heats the solution in the evaporation barrel. The bottom of the drum is provided with an electric heating device for assisting solar heating. The solid substance obtained after the evaporation of the precipitation waste is uranium mixture, and can be used for subsequent purification.
The solar concentrating reflector is made of high-reflection coefficient materials into a hemispherical shape and is fixed on the support, the spherical surface faces the sun in the south, and the reflected light is focused on the black surface of the precipitation waste thermal evaporation tank, so that the maximum heating effect is achieved.
The uranium removal rate testing process comprises the following steps: measuring a certain amount of wastewater solution from the PH regulating tank by using a dividerSpectrophotometry for determining residual U (VI) concentration C 0 The method comprises the steps of carrying out a first treatment on the surface of the Taking a certain amount of supernatant from the three-dimensional electrolytic cell, and spectrophotometrically measuring the concentration C of the residual U (VI) t . The uranium removal rate R is calculated according to the following formula: r= (C 0 -C t )/C 0
The beneficial effects of the invention are as follows: (1) The device has the advantages that the removal rate of uranyl ions in the low-concentration uranium waste liquid with the concentration of less than 10mg/L can reach 99.8%, the residual quantity is lower than the national safety discharge standard (0.05 mg/L), and the device can be used as the safety discharge of uranium reaching the standard water. (2) in a three-dimensional electrochemical device: the introduction of the modified NZVI material as a particle electrode can doubly improve the electrolysis efficiency, so that the electrolysis process which originally needs more than 4 hours is shortened to 1 hour. (3) In the solar energy enrichment area, the adoption of the solar cell panel and the solar concentrating spherical mirror can ensure that the whole device does not need to consume other energy sources. (4) The automatic control module controls the automatic feeder, the low-frequency stirrer, the wastewater inlet and outlet valves and the like, and the whole treatment process does not need manual operation, so that the method is energy-saving, efficient and environment-friendly. (5) The device can be expanded into a plurality of devices which work simultaneously, and the working efficiency is greatly improved.
Drawings
FIG. 1a is an SEM image of an unmodified NZVI;
FIG. 1b is an SEM image of a modified NZVI prepared in accordance with an embodiment of the invention;
fig. 2 is a schematic general structure of the present invention.
Fig. 3 is a schematic cross-sectional view of a three-dimensional electrochemical device according to the present invention.
Fig. 4 is a schematic top view of a three-dimensional electrochemical device according to the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. All techniques implemented based on the above description of the invention are within the scope of the invention.
The preparation steps of the raw material modified NZVI material (coated NZVI/high-strength powder) required by the invention are as follows:
1, preparing FeCl3 solution; 2, preparing high-gluten powder of the wrapping raw materials; and 3, preparing the coated composite material NZVI/high-strength powder.
The preparation process comprises the following steps: accurately measuring 15mL of ethanol, and adding 35mL of water to obtain 30% absolute ethanol; 50mL of 30% absolute ethanol was weighed into a conical flask, and 4.83g of FeCl was weighed 3 Placing 6H2O in a conical flask, mixing with 30% absolute ethanol, and stirring to obtain FeCl 3 A solution; weighing 20 g of common high-gluten powder, grinding for 15min by using a ball mill, and sieving by a 100-mesh sieve to obtain a high-gluten powder raw material. Accurately weighing 2g of high-gluten powder raw material and adding the high-gluten powder raw material into FeCl 3 Stirring the solution for 1h on a magnetic stirrer; weighing 4.32g KBH4 in 100mL H2O to prepare 0.8mol/L KBH4 solution, slowly adding the solution into a FeCl3 solution conical flask, continuously stirring the solution with black foam during the adding, and stirring the solution for 30min to obtain nano zero-valent iron solution coated on high-strength steel powder; and respectively washing the nano zero-valent iron solution with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 65 ℃ to obtain coated NZVI/high-strength powder.
SEM characterization of the structure and morphology of the modified NZVI powder: in FIG. 1, FIG. 1a is an uncoated NZVI showing that the nano zero-valent iron particles are 80-100 nm in size, are spherical and chain-like and are clustered together, and this cluster reduces reactivity and limits mobility. FIG. 1b is NZVI coated with high-strength steel powder, and shows that the particle size of the modified material is 80-100 nm, the modified material is spherical and has good dispersibility, which shows that the introduction of the coated material can effectively inhibit the agglomeration of nano zero-valent iron, increase the reaction surface area and increase the reaction active sites, and can be introduced into a three-dimensional electrochemical device as a high-quality particle electrode.
As shown in fig. 2 to 4, the device for recycling uranium in nuclear wastewater by using a solar energy-based modified NZVI three-dimensional electrochemical method comprises a wastewater PH adjusting tank 1, an electrolysis device connected with the wastewater PH adjusting tank 1, an automatic feeder connected with the top of the electrolysis device and a precipitation waste thermal evaporation tank 17 connected with the bottom of the electrolysis device, wherein the electrolysis device comprises an electrolysis tank 9, an electrolysis cathode 11 and an electrolysis anode 13 are arranged in the electrolysis tank 9, the electrolysis anode 13 is made of inert graphite, the electrolysis cathode 11 is an iron flocculating electrode, the electrolysis cathode 11 and the electrolysis anode 13 are connected with a power supply, the bottom of the electrolysis tank 9 is in a funnel shape, the bottom of the electrolysis tank 9 is connected with the precipitation waste thermal evaporation tank 17 through a precipitation waste outlet pipe 21, and the top of the electrolysis tank 9 is connected with a supernatant fluid delivery pipe 22;
the waste water PH regulating tank 1 is provided with a waste liquid inlet pipe 2 and a waste liquid outlet pipe 23, and the waste liquid outlet pipe 23 is positioned at the bottom of the waste water PH regulating tank 1 and is communicated with the electrolytic tank 9;
the automatic feeder comprises a modified NZVI powder feeding box 4, wherein the modified NZVI powder feeding box 4 is connected with a funnel pipe 8 through a modified NZVI powder feeding pipe 24, and the bottom of the funnel pipe 8 is connected with an electrolytic cell 9.
Wherein nuclear wastewater is introduced into a wastewater pH adjusting tank 1 through a wastewater inlet pipe 2 by HNO 3 Or NaOH adjusts the ph=5 of the solution, and modified NZVI material (coated NZVI/high-gluten powder) is stored in the modified NZVI powder charging box 4.
Further, an electric heating device 18 is arranged at the bottom of the precipitation waste heat evaporation tank 17, the electric heating device 18 is an electric heating wire which is arranged at the bottom of the precipitation waste heat evaporation tank 17 in an annular arrangement, a solar concentrating mirror 20 is arranged on one side of the precipitation waste heat evaporation tank 17, the solar concentrating mirror 20 is hemispherical and fixed on a support, the spherical surface faces the sun in the south, and reflected light of the solar concentrating mirror 20 is focused on the surface of the precipitation waste heat evaporation tank 17.
The surface of the precipitation waste heat evaporation tank 17 is coated with a black coating, and the black coating adopts a heat absorbing material. A low-frequency stirrer 10 is arranged in the electrolytic cell 9, and the low-frequency stirrer 10 is powered on.
The waste water PH regulating tank 1 and the electrolytic tank 9 are arranged on a base 19, a solar cell panel 7 is arranged on the base 19, and the solar cell panel 7 is connected with the automatic control module 6.
The waste liquid outlet pipe 23 is provided with a control valve 3, the supernatant liquid outlet pipe 22 is provided with a control valve 16, the modified NZVI powder supply pipe 24 is provided with a control valve 5, and the precipitation waste outlet pipe 21 is provided with a control valve 16.
The automatic control module 6 includes a battery connected to the solar panel 7, a solar controller connected to the battery, and a valve controller. The model of the solar controller is SR602, and the storage battery is connected with the electrolytic cathode, the electrolytic anode, the electric heating device and the low-frequency stirrer; the model of the valve controller is DATA-6321, and the valve controller is connected with the control valve on the waste liquid outlet pipe, the supernatant liquid outlet pipe, the modified NZVI powder supply pipe and the precipitation waste outlet pipe.
The corresponding operation steps of the device are as follows: (1) The high-gluten powder is used as a carrier, and a liquid phase reduction method is adopted to prepare the coated NZVI/high-gluten powder. (2) The modified NZVI material (coated NZVI/high-strength powder) is used as a particle electrode, inert graphite is used as an anode, and an iron flocculation polar plate is used as a cathode to build a three-dimensional electrolytic cell. (3) The solar panel is used as a photovoltaic conversion device to provide required electric power for the three-dimensional electrochemical device. (4) The drum coated with black heat absorbing material is used as a precipitation waste treatment tank, the solar concentrating mirror is used as a photo-thermal conversion device to thermally evaporate precipitation waste, and the obtained solid substance is uranium mixture. (5) After the electrolytic reaction for 60min, the residual uranium content in the supernatant of the three-dimensional electrolytic cell is lower than the national safety discharge standard, and the uranium can be used as the standard water for safety discharge.
The modified NZVI composite material is used as a particle electrode of a three-dimensional electrochemical device, and has the advantages of small particle size, good dispersibility and large reaction surface area.
The modified NZVI is used as a particle electrode, and the particle electrode, the graphite inert electrode and the iron flocculation electrode form a three-dimensional electrode system. Inert graphite is used as an anode, and an iron flocculating electrode is used as a cathode. The iron ions are converted into ferroferric oxide through electrolytic reduction reaction, hexavalent uranium U (VI) in the nuclear waste liquid is reduced into tetravalent uranium U (IV), and the tetravalent uranium U (IV) and the ferroferric oxide are subjected to condensation coprecipitation. The power consumption required by the electrochemical device is powered by a solar-charged storage battery;
an automatic feeder is arranged for feeding the modified NZVI powder at fixed time and fixed quantity. The time and weight of the feed are set by the valve controller. The low-frequency stirrer is arranged above the electrolysis device, the rotation frequency is lower than 10 revolutions per second, and the electrolytic reaction and the coagulation and precipitation process can be accelerated. The required power consumption is powered by a solar charged battery.
The solar panel adopts the 140W amorphous silicon solar panel, and in a solar energy enrichment area, the generated power can meet the electric energy requirement of an electrolysis and automatic control circuit. The automatic control module is divided into an electrolysis circuit, an automatic feeder control circuit, a low-frequency stirrer control circuit and a solar automatic tracking device. The automatic control module power consumption is supplied by a solar charging storage battery, and the automatic control module and the solar panel are arranged on the same bracket.
The precipitation waste heat evaporation tank is a barrel with the diameter of 0.5 m and the height of 1 m, the outer surface of the barrel is coated with black heat absorption paint, and the black paint of the barrel strongly absorbs reflected sunlight and heats the solution in the evaporation barrel. The bottom of the drum is provided with an electric heating device for assisting solar heating. The solid substance obtained after the evaporation of the precipitation waste is uranium mixture, and can be used for subsequent purification.
The solar concentrating reflector is made of high-reflection coefficient materials into a hemispherical shape and is fixed on the support, the spherical surface faces the sun in the south, and the reflected light is focused on the black surface of the precipitation waste thermal evaporation tank, so that the maximum heating effect is achieved.
In a specific operation, the waste liquid to be treated enters the waste water PH regulating tank 1 through the waste liquid inlet pipe 2, the PH value of the solution is regulated to be=5 by HNO3 or NaOH, the regulated waste liquid flows into the electrolytic tank 9 through the waste liquid outlet pipe 23, then the automatic feeder is controlled by the automatic control module 6 to put modified NZVI powder into the electrolytic tank 9, and in the process of putting the modified NZVI powder, the rotation frequency of the low-frequency stirrer 10 is lower than 10 revolutions per second, so that the electrolytic reaction and the coagulation sedimentation process can be accelerated. The electrolytic cell 9 uses the modified NZVI as a particle electrode, and forms a three-dimensional electrode system with a graphite inert electrode and an iron flocculation electrode respectively. Inert graphite is used as an anode, and an iron flocculating electrode is used as a cathode. Converting iron ions into ferroferric oxide through electrolytic reduction reaction, reducing hexavalent uranium U (VI) into tetravalent uranium U (IV), performing condensation coprecipitation with the ferroferric oxide, pumping the precipitation waste into a precipitation waste thermal evaporation tank 17 through a precipitation waste outlet pipe 21, and discharging supernatant in an electrolytic tank 9 through a supernatant delivery pipe 22; the solid matter obtained after the precipitation waste in the precipitation waste thermal evaporation tank 17 is uranium mixture, and can be used for subsequent purification.
In addition, a certain amount of wastewater solution is measured from the PH regulating tank by spectrophotometryDetermining the concentration C of residual U (VI) in the solution 0 The method comprises the steps of carrying out a first treatment on the surface of the Taking a certain amount of supernatant from the three-dimensional electrolytic cell, and spectrophotometrically measuring the concentration C of the residual U (VI) t The method comprises the steps of carrying out a first treatment on the surface of the The uranium removal rate R is calculated according to the following formula: r= (C 0 -C t )/C 0 . The device has the advantages that under the condition of rich solar energy, solution PH=5 and electrolysis voltage U=3V, after the electrolysis reaction for 60min, the uranium removal rate R in the supernatant fluid can reach 99.8%, and the device can be used as safe discharge of uranium reaching the standard water.
In a three-dimensional electrochemical device: the introduction of the modified NZVI material as a particle electrode can doubly improve the electrolysis efficiency, so that the electrolysis process which originally needs more than 4 hours is shortened to 1 hour. In the solar energy enrichment area, the adoption of the solar cell panel and the solar concentrating spherical mirror can ensure that the whole device does not need to consume other energy sources. The automatic control module controls the automatic feeder, the low-frequency stirrer, the wastewater inlet and outlet valves and the like, and the whole treatment process does not need manual operation, so that the method is energy-saving, efficient and environment-friendly. The device can be expanded into a plurality of devices which work simultaneously, and the working efficiency is greatly improved.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The device for recycling uranium in nuclear wastewater by using a solar energy-based modified NZVI three-dimensional electrochemical method comprises a wastewater PH regulating tank, an electrolysis device connected with the wastewater PH regulating tank, an automatic feeder connected with the top of the electrolysis device and a precipitation waste thermal evaporation tank connected with the bottom of the electrolysis device, and is characterized in that the electrolysis device comprises an electrolysis tank, an electrolysis cathode and an electrolysis anode are arranged in the electrolysis tank, the electrolysis cathode and the electrolysis anode are connected with a power supply, the bottom of the electrolysis tank is in a funnel shape, the bottom of the electrolysis tank is connected with the precipitation waste thermal evaporation tank through a precipitation waste outlet pipe, and the top of the electrolysis tank is connected with a supernatant delivery pipe;
the waste water PH regulating tank is provided with a waste liquid inlet pipe and a waste liquid outlet pipe, and the waste liquid outlet pipe is positioned at the bottom of the waste water PH regulating tank and is communicated with the electrolytic tank;
the automatic feeder comprises a modified NZVI powder feeding box, wherein the modified NZVI powder feeding box is connected with a funnel pipe through a modified NZVI powder supply pipe, and the bottom of the funnel pipe is connected with an electrolytic cell;
the modified NZVI powder charging box is put into the electrolytic cell, and is used as a particle electrode, and respectively forms a three-dimensional electrode system with an electrolytic cathode and an electrolytic anode in the electrolytic cell; the iron ions are converted into ferroferric oxide through electrolytic reaction, hexavalent uranium U (VI) in nuclear waste liquid is reduced into tetravalent uranium U (IV), and the tetravalent uranium U (IV) and the ferroferric oxide undergo condensation coprecipitation,
the preparation process of the modified NZVI powder comprises the following steps: accurately measuring 15mL of ethanol, and adding 35mL of water to obtain 30% absolute ethanol; 50mL of 30% absolute ethanol was weighed into a conical flask, and 4.83g of FeCl was weighed 3 ·6H 2 Placing O in a conical flask, mixing with 30% absolute ethanol, and stirring to obtain FeCl 3 A solution; weighing 20 g of common high-gluten powder, grinding for 15min by using a ball mill, and sieving by a 100-mesh sieve to obtain a high-gluten powder raw material; accurately weighing 2g of high-gluten powder raw material and adding the high-gluten powder raw material into FeCl 3 Stirring the solution for 1h on a magnetic stirrer; weigh 4.32g KBH 4 At 100mL H 2 0.8mol/L KBH in O 4 Solution and slow addition of FeCl 3 Continuously stirring the solution in a solution conical flask along with black foam during adding, and stirring for 30min to obtain a nano zero-valent iron solution coated on high-strength powder; and respectively washing the nano zero-valent iron solution with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 65 ℃ to obtain coated NZVI/high-strength powder.
2. The device for recycling uranium in nuclear wastewater by using a solar-based modified NZVI three-dimensional electrochemical method according to claim 1, wherein the electrolytic anode is made of inert graphite, and the electrolytic cathode is an iron flocculating electrode.
3. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 1 or 2, wherein an electric heating device is arranged at the bottom of the precipitation waste heat evaporation tank, a solar concentrating mirror is arranged on one side of the precipitation waste heat evaporation tank, the solar concentrating mirror is hemispherical and fixed on a support, the spherical surface faces south towards the sun, and reflected light of the solar concentrating mirror is focused on the surface of the precipitation waste heat evaporation tank.
4. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 3, wherein a black coating is coated on the surface of the precipitation waste thermal evaporation tank, and the black coating is made of a heat absorbing material.
5. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 3, wherein a low-frequency stirrer is arranged in the electrolytic cell and is powered on.
6. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 5, wherein the wastewater PH adjusting tank and the electrolytic tank are arranged on a base, a solar panel is arranged on the base, and the solar panel is connected with an automatic control module.
7. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 6, wherein a control valve is arranged on the waste liquid outlet pipe, the supernatant liquid outlet pipe, the modified NZVI powder supply pipe and the precipitation waste outlet pipe.
8. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 7, wherein the automatic control module includes a storage battery connected with a solar panel, a solar controller connected with the storage battery, and a valve controller.
9. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 8, wherein the type of the solar controller is SR602, and the storage battery is connected with an electrolytic cathode, an electrolytic anode, an electric heating device and a low-frequency stirrer;
the model of the valve controller is DATA-6321, and the valve controller is connected with the control valve on the waste liquid outlet pipe, the supernatant liquid outlet pipe, the modified NZVI powder supply pipe and the precipitation waste outlet pipe.
10. The device for recycling uranium in nuclear wastewater by using a modified NZVI three-dimensional electrochemical method based on solar energy according to claim 3, wherein the electric heating device is an electric heating wire which is arranged at the bottom of the precipitation waste thermal evaporation tank in an annular mode.
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