CN109065202B - System and method for treating radioactive nuclear waste organic phase - Google Patents
System and method for treating radioactive nuclear waste organic phase Download PDFInfo
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- CN109065202B CN109065202B CN201810856804.XA CN201810856804A CN109065202B CN 109065202 B CN109065202 B CN 109065202B CN 201810856804 A CN201810856804 A CN 201810856804A CN 109065202 B CN109065202 B CN 109065202B
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- 239000012074 organic phase Substances 0.000 title claims abstract description 130
- 239000002699 waste material Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 134
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 127
- 230000003647 oxidation Effects 0.000 claims abstract description 111
- 230000003197 catalytic effect Effects 0.000 claims abstract description 72
- 238000001704 evaporation Methods 0.000 claims abstract description 56
- 230000008020 evaporation Effects 0.000 claims abstract description 54
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000012071 phase Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 30
- -1 phosphate radical Chemical class 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 239000010452 phosphate Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000007865 diluting Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 65
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 39
- 239000003995 emulsifying agent Substances 0.000 claims description 22
- 239000002351 wastewater Substances 0.000 claims description 20
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000004064 recycling Methods 0.000 claims description 14
- 229910003460 diamond Inorganic materials 0.000 claims description 13
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 claims description 9
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010955 niobium Substances 0.000 claims description 4
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- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
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- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012875 nonionic emulsifier Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
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- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 abstract description 2
- VBWSWBQVYDBVGA-UHFFFAOYSA-N uranium Chemical compound [U].[U].[U] VBWSWBQVYDBVGA-UHFFFAOYSA-N 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000002901 radioactive waste Substances 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical group [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/08—Processing by evaporation; by distillation
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a system and a method for treating a radioactive nuclear waste organic phase. The treatment system comprises a pretreatment unit, a wet catalytic oxidation treatment unit, an electrolytic oxidation treatment unit and an evaporation concentration treatment unit which are sequentially connected. In the treatment process, the waste organic phase is firstly subjected to pretreatment such as mixing, diluting, dosing, stirring and the like by a pretreatment unit, and then enters a wet catalytic oxidation unit to carry out COD (chemical oxygen demand) in the waste organic phase cr Most of organic matters are catalyzed and oxidized into inorganic matters or macromolecules are catalyzed and oxidized into small molecules; the water after wet catalytic oxidation treatment enters an electrolytic oxidation treatment unit for advanced oxidation treatment, and finally the organic phase is completely converted into an inorganic phase, so that the oil is thoroughly changed into water; because the treated water contains a small amount of radioactive uranium, phosphate radical, nitrate radical ions and the like, the uranium, the phosphate radical and the nitrate radical are recovered through an evaporation and concentration treatment unit; effectively solves the technical problems of the nuclear industry for many years and the potential safety hazard of long-term storage of the waste organic phase.
Description
Technical Field
The invention relates to the technical field of nuclear environmental protection, in particular to a system and a method for treating radioactive nuclear waste organic phase.
Background
The nuclear science technology is widely applied to a plurality of fields such as industry, agriculture, medicine, military and the like, brings great convenience and benefit to the production and life of people, has important influence on the health of people, the safety of environment and the development of offspring, has become a topic of general attention of people, and the Japanese Fudao nuclear accident occurring in the past causes more anxiety to the nuclear safety. In the development and utilization process of the nuclear science technology, a large amount of radioactive waste is generated, radioactive waste organic matters are equal, and the radioactive waste water causes water and soil pollution after entering the environment and can enter the human body through various ways, so that serious harm is caused to the environment and human beings.
Extraction of uranium from uranium ores generally employs leaching methods, i.e., chemical reagents are used to convert the useful component uranium, etc. in the ore into soluble compounds, and then metals, such as the useful component uranium, are recovered from the solution. Methods for extracting uranium from leachate generally include an ion exchange method, a chemical precipitation method and a solvent extraction method. The solvent extraction method is to utilize an organic solvent (called an organic phase) to be mixed and contacted with uranium-containing leaching solution (called an aqueous phase), so that uranium in the aqueous phase is extracted into the organic phase, and then back-extracted into the aqueous phase, thereby separating impurities and achieving the extraction purpose. In the solvent extraction method, a TBP extraction process flow is generally adopted, an extracting agent is tributyl phosphate, sulfonated kerosene is used as a diluent, an organic phase is formed by tributyl phosphate and sulfonated kerosene, uranium in the leaching solution is transferred into the organic phase, the organic phase containing uranium is subjected to back extraction after being purified, the back extracting agent is a 10% dilute nitric acid solution, and the uranium is transferred into a back extracting solution (finished product solution) to enter the next unit for treatment. The lean organic phase is regenerated by the regenerant and then returned to the front section to continuously extract the uranium phase in the leaching solution (raffinate) for recycling; as shown in fig. 1.
After the organic phase is extracted, organic phase solutions are contained in a raffinate phase, a loaded organic phase washing liquid, an organic phase-poor regeneration liquid and an organic phase recovery tail liquid, and waste organic phases which cannot be reused are finally generated after repeated reuse, and are collectively called waste organic phases. The amount of waste organic phase produced is about tens of tons per year, based on 1000tU/a uranium conversion. Also present in the spent organic phase are small amounts of uranium compounds (or corresponding ions), tributyl phosphate sulphonated kerosene and residual nitric acid, the ratio of sulphonated kerosene to monobutyl phosphate being about 7:3. The waste organic phases have great difficulty in recycling, transportation and treatment because of containing a small amount of uranium, and nuclear pollution is generated by incineration. Recovery is difficult and very uneconomical, and has high cost, low yield and relatively complex process. Since the main body of the solution is basically waste organic phase and contains radioactive elements, the solution is inflammable by open fire, which brings potential risks for long-term storage, but the storage is still mainly carried out until now.
At present, no better solution exists for thoroughly treating the waste organic phase at home and abroad, and the solution becomes a worldwide difficult problem.
Disclosure of Invention
In view of the shortcomings in the prior art, the present invention is directed to a system and method for treating a radioactive spent organic phase. The radioactive nuclear waste organic phase treatment system provided by the invention has the advantages of high equipment degree, mature technology of each section, low energy consumption, thorough treatment of the waste organic phase and the like, and can successfully realize the change of an oil phase into a water phase; meanwhile, the invention does not produce secondary pollution in the treatment process, can realize the recovery and reutilization of uranium, and effectively solves the technical problems which are not solved for many years in the nuclear industry and the potential safety hazard caused by long-term storage of waste organic phase.
In a first aspect, the present invention provides a system for the treatment of a radioactive nuclear waste organic phase comprising: the device comprises a pretreatment unit, a wet catalytic oxidation unit and an electrolytic oxidation unit; wherein the pretreatment unit, the wet catalytic oxidation treatment unit and the electrolytic oxidation treatment unit are sequentially connected; the pretreatment unit is used for diluting the waste organic phase to obtain a uniform waste organic phase; the wet catalytic oxidation treatment unit is used for oxidizing the uniform waste organic phase to primarily degrade COD in the waste organic phase cr Obtaining catalytic oxidation wastewater; the electrolytic oxidation treatment unit is used for further removing COD in the catalytic oxidation wastewater cr . The radioactive nuclear waste organic phase is treated by the units in sequence to finally realize the phase change of oil into water phase, and the COD of produced water after electrolysis cr Reaching the first-level discharge standard of industrial sewage; meanwhile, the treatment system fully recycles a small amount of uranium, and no secondary pollution is generated in the treatment process.
Firstly, the organic phase with the radioactive nuclear waste is subjected to pretreatment such as mixing, dilution, dosing, stirring and the like through a pretreatment unit; then enters a wet catalytic oxidation unit to carry out COD in the waste organic phase cr Is large in sizeCatalytic oxidation of part of organic matter into inorganic matter or macromolecular matter into micromolecular matter; and then the water after wet catalytic oxidation treatment enters an electrolytic oxidation treatment unit for further advanced oxidation treatment, and finally organic matters are converted into inorganic matters, namely the organic phase is completely converted into inorganic phase (water phase), so that the oil-to-water conversion is thoroughly realized.
Preferably, the pretreatment unit comprises a liquid inlet system, a mixing system and a dosing system; the mixing system is respectively connected with the liquid inlet system and the dosing system, and the dosing system is used for placing the emulsifying agent.
Preferably, the wet catalytic oxidation treatment unit comprises a preheater, a reactor, a condenser and a gas-liquid separator which are connected in sequence; wherein the preheater is used for preheating the uniform waste organic phase; the reactor is used for carrying out catalytic oxidation reaction on the preheated uniform waste organic phase; the gas-liquid separator is used for separating catalytic oxidation reaction products to obtain catalytic oxidation wastewater and gas-phase products; more preferably, the preheater is an energy recovery in the form of a shell and tube electric heater, such as a shell and tube electric heater; the outlet of the gas-liquid separator adopts an automatic pneumatic needle valve.
Preferably, the electrolytic oxidation treatment unit comprises an electrode device and a reaction tank; wherein, the electrode is a diamond electrode (BDD), and the material of the diamond electrode is preferably boron-doped diamond (BDD/niobium-electrode) coated on the surface of the metal niobium; more preferably, the positive and negative electrode plates of the electrode device are the same in material and form, and are used for realizing instant mutual automatic switching of the positive electrode and the negative electrode by changing current; still more preferably, the reaction tank is a plurality of reaction tanks connected in parallel, and preferably three; specifically, the reaction tank is a first reaction tank, a second reaction tank and a third reaction tank which are connected in parallel, the first reaction tank is used for water inflow, the second reaction tank is used for circulating electrolysis, and the third reaction tank is used for water drainage.
Preferably, the treatment system further comprises an evaporative concentration treatment unit; the evaporation concentration treatment unit is connected with the electrolytic oxidation treatment unit and is used for removing phosphate ions, uranium and nitrate ions in the electrolyzed water; more preferably, the evaporative concentration processing unit comprises a first dosing reaction system, a second dosing reaction system and a low-temperature evaporative concentration system which are connected in sequence; the first chemical adding reaction system is used for removing phosphate radical in the water after the electrolytic treatment, the second chemical adding reaction system is used for removing uranium in the water after the electrolytic treatment, and the evaporation concentration system is used for removing ammonium nitrate in the water after the electrolytic treatment; still more preferably, the evaporation and concentration system is provided with a water outlet which is connected with a liquid inlet system of the pretreatment unit through a pipeline; still preferably, the evaporative concentration processing unit employs a cryogenic evaporative concentration system, and the temperature of the cryogenic evaporative concentration system does not exceed 70 ℃.
In a second aspect, the present invention provides a method for treating a radioactive nuclear waste organic phase, using a treatment system of the present invention, comprising the steps of: s1: the waste organic phase enters a pretreatment unit, and is uniformly stirred with water and an emulsifying agent in a mixing system to form a uniform waste organic phase; s2: the uniform waste organic phase enters a wet catalytic oxidation treatment system, catalytic oxidation reaction is carried out in a reactor after preheating, and then a reaction product is treated by a gas-liquid separator to respectively obtain catalytic oxidation wastewater and a gas-phase product; wherein, the COD of the produced water after wet catalytic oxidation treatment cr The removal rate can reach 50% -85%; s3: the catalytic oxidation wastewater enters an electrolytic oxidation treatment unit to further remove the residual COD in the wastewater cr Obtaining water after electrolytic treatment; wherein the COD of the water after electrolytic treatment cr Meets the national sewage discharge standard requirements; preferably, step S4 is further included after S3: and (3) feeding the electrolyzed water into an evaporation concentration treatment unit, and sequentially recovering phosphate ions, uranium and nitrate ions in the electrolyzed water to finally obtain a product water phase, so as to realize oil phase change into the water phase.
Preferably, in S1: the adding amount of the emulsifier is 2-5% of the mass of the waste organic phase, and the stirring speed is 150-250 rpm; more preferably, the emulsifier is selected from nonionic emulsifiers, preferably ethylene oxide adducts of sorbitan fatty acid esters, and even more preferably one or more of tween 20, tween 60 and tween 80.
Preferably, in S2: the conditions for the catalytic oxidation reaction specifically include: the pressure is 5-9 MPa, preferably 9MPa; the temperature is 250-270 ℃, preferably 270 ℃; the time is 1 to 2 hours, preferably 2 hours; the raw material components of the catalyst comprise a carrier, an active component and an auxiliary agent; preferably, the carrier of the catalyst is anatase titanium dioxide; noble metals are used for the active component, and the noble metals are preferably ruthenium and/or platinum; the auxiliary agent is rare earth elements, and the rare earth elements are preferably cerium and/or lanthanum.
Preferably, in S3: the electrolytic oxidation condition is a constant current condition, and the electrolytic current is 100-1000A, preferably 1000A; the electrolysis time is 4 to 8 hours, preferably 4 hours.
Preferably, in S4: adding quick lime into the first dosing stirring reaction system to remove phosphate radicals, and recycling generated calcium phosphate; adding ammonia water into the second dosing stirring reaction system to obtain ammonium diuranate precipitate and water containing ammonium nitrate, and returning the generated ammonium diuranate precipitate to a uranium purification and conversion process section for recycling; feeding the produced water containing ammonium nitrate into a low-temperature evaporation concentration system for evaporation concentration crystallization to obtain ammonium nitrate and evaporated concentrated produced water; more preferably, ammonium nitrate is recovered, one part of the produced water after evaporation and concentration is discharged, and the other part of the produced water returns to a liquid inlet system of the pretreatment unit; still more preferably, in the second dosing and stirring reaction system, ammonia is added until the online monitoring solution pH value is equal to 7; the temperature of the low-temperature evaporation concentration system is not higher than 70 ℃.
The radioactive nuclear waste organic phase treatment system provided by the invention has the advantages of high equipment degree, mature technology of each section, low energy consumption, thorough treatment of the waste organic phase and the like, and can successfully realize the change of an oil phase into a water phase; meanwhile, the invention does not produce secondary pollution in the treatment process, can realize the recovery and reutilization of uranium, and effectively solves the technical problems which are not solved for many years in the nuclear industry and the potential safety hazard caused by long-term storage of waste organic phase.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the embodiments or the drawings needed in the prior art, and it is obvious that the drawings described below are some embodiments of the present invention and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of an extraction process in the background of the invention section;
FIG. 2 is a schematic diagram of a system for treating radioactive nuclear waste organic phases according to an embodiment of the present invention;
FIG. 3 is a graph showing the variation of the moisture content of saturated humid air at different temperatures in an embodiment of the present invention;
FIG. 4 is a graph of saturated vapor pressure of water vapor at different temperatures in an embodiment of the present invention;
reference numerals:
1-waste organic phase liquid inlet pump, 2-emulsifier liquid inlet pump, 3-air compressor, 4-steel cylinder buffer tank, 5-mixing system, 6-wet catalytic oxidation liquid inlet pump, 7-preheater, 8-reactor, 9-condenser, 10-gas-liquid separator, 11-buffer tank, 12-electrolytic oxidation liquid inlet pump, 13-reaction tank, 14-electrode, 15-circulating pump, 16-electrolytic oxidation liquid outlet pump, 17-first mixing and stirring precipitation tank, 18-second mixing and stirring precipitation tank and 19-low temperature evaporation and concentration system.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and the examples are not construed as specifying specific conditions, either as conventional conditions or as suggested by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The present embodiment provides a treatment system for a radioactive nuclear waste organic phase, comprising: the device comprises a pretreatment unit, a wet catalytic oxidation unit and an electrolytic oxidation unit; wherein, pretreatment unit, wet catalytic oxidation unit and wet catalytic oxidation unitThe electrolytic oxidation treatment units are connected in sequence; the pretreatment unit is used for diluting the waste organic phase to obtain a uniform waste organic phase; the wet catalytic oxidation treatment unit is used for oxidizing the uniform waste organic phase to primarily degrade COD in the waste organic phase cr Obtaining catalytic oxidation wastewater; the electrolytic oxidation treatment unit is used for further removing COD in the catalytic oxidation wastewater cr 。
Firstly, the organic phase with the radioactive nuclear waste is subjected to pretreatment such as mixing, dilution, dosing, stirring and the like through a pretreatment unit; then enters a wet catalytic oxidation unit to carry out COD in the waste organic phase cr Most of organic matters are catalyzed and oxidized into inorganic matters or macromolecules are catalyzed and oxidized into small molecules; and then the water after wet catalytic oxidation treatment enters an electrolytic oxidation treatment unit for further advanced oxidation treatment, and finally organic matters are converted into inorganic matters, namely the organic phase is completely converted into inorganic phase (water phase), so that the oil-to-water conversion is thoroughly realized. The dilution of the organic phase is due to COD of the waste organic phase cr The concentration is too high, and the reactor in the subsequent wet catalytic oxidation treatment unit is easy to fly temperature and difficult to control without dilution treatment.
Specifically, the pretreatment unit comprises a liquid inlet system, a mixing system and a dosing system; the mixing system is respectively connected with the liquid inlet system and the dosing system, and the dosing system is used for placing the emulsifying agent; since the waste organic phase belongs to an oil phase and is not water-miscible, an emulsifier needs to be added so that the waste organic phase is completely mixed with water and emulsified in a stirred state to form a uniform waste organic phase.
Specifically, the wet catalytic oxidation treatment unit comprises a preheater, a reactor, a condenser and a gas-liquid separator which are connected in sequence; wherein the preheater is used for preheating the uniform waste organic phase; the reactor is used for carrying out catalytic oxidation reaction on the preheated uniform waste organic phase; the gas-liquid separator is used for separating catalytic oxidation reaction products to obtain catalytic oxidation wastewater and gas-phase products; preferably, the preheater is an energy recoverer in the form of a shell and tube electric heater; the outlet of the gas-liquid separator adopts an automatic pneumatic needle valve. Directly discharging the gas phase products generated after the reaction, such as carbon dioxide, nitrogen and the like, through wet methodCOD of produced water after catalytic oxidation treatment cr The removal rate can reach 50% -85%, and then the produced water is fed into the next treatment unit (electrolytic oxidation treatment unit) for advanced treatment.
Specifically, the electrolytic oxidation treatment unit is provided with an electrode device; the electrode is a diamond electrode, and the material of the diamond electrode is preferably boron-doped diamond coated on the surface of the metal niobium; preferably, the positive and negative electrode plates of the electrode device are the same in material and form, and are used for realizing instant mutual automatic switching of the positive electrode and the negative electrode by changing current. Further treating the water produced after the wet catalytic oxidation treatment to remove the corresponding residual COD cr And the COD of the water after the electrolytic treatment cr Completely meets the national sewage discharge standard requirements.
Specifically, the treatment system further comprises an evaporation concentration treatment unit; the evaporation concentration treatment unit is connected with the electrolytic oxidation treatment unit and is used for removing phosphate ions, uranium and nitrate ions in the electrolyzed water; further, the evaporation concentration treatment unit comprises a first dosing reaction system, a second dosing reaction system and a low-temperature evaporation concentration system which are sequentially connected; the first chemical adding reaction system is used for removing phosphate radical in the water after the electrolytic treatment, the second chemical adding reaction system is used for removing uranium in the water after the electrolytic treatment, and the evaporation concentration system is used for removing ammonium nitrate in the water after the electrolytic treatment; further, a water outlet is arranged on the evaporation concentration system and is connected with a feed inlet of the pretreatment unit through a pipeline; still further, the evaporative concentration processing unit adopts a low-temperature evaporative concentration system, and the temperature of the low-temperature evaporative concentration system is not more than 70 ℃.
Adding quick lime serving as a medicament into a mixing and precipitating tank of the first chemical adding reaction system, so as to effectively remove phosphate radical in the electrolyzed water, wherein the adding amount of the quick lime is determined according to the content of the online monitoring phosphate radical; adding ammonia water into a mixed precipitation tank of the second dosing reaction system to obtain ammonium diuranate precipitate and produced water containing ammonium nitrate, and adding the ammonia water until the pH value of the online monitoring solution is equal to 7; then, the generated ammonium diuranate precipitate is recovered, and the recovered ammonium diuranate can be returned to a uranium purification and conversion process section for recycling; the produced water containing ammonium nitrate enters a low-temperature evaporation concentration system to be evaporated, concentrated and crystallized to obtain ammonium nitrate and evaporated and concentrated produced water, and the evaporated and concentrated produced water is neutral and can be directly discharged outwards or returned to a mixing system of a pretreatment unit through a pipeline to be used as raw water for diluting an original waste organic phase so as to be recycled.
In the treatment process, the radioactive nuclear waste organic phase is firstly subjected to pretreatment such as mixing, diluting, dosing, stirring and the like by a pretreatment unit, and then enters a wet catalytic oxidation unit to carry out COD in the waste organic phase cr Most of the organic matters are catalyzed and oxidized into inorganic matters or macromolecules are catalyzed and oxidized into small molecules. The water after wet catalytic oxidation treatment enters an electrolytic oxidation treatment unit for further advanced oxidation treatment, and finally organic matters are converted into inorganic matters, namely the organic phase is completely converted into inorganic phase (water phase), so that the oil-to-water conversion is thoroughly realized, and the treated water contains a small amount of radioactive uranium, phosphate radical, nitrate radical ions and the like, so that uranium, phosphate radical and nitrate radical are recycled and reused through an evaporation concentration treatment unit. It should be noted that, during start-up, because no produced water of the evaporation concentration unit returns to the pretreatment unit, a certain amount of deionized water can be added, and when the produced water is evaporated and concentrated, the produced water of the evaporation and concentration can be directly introduced, so that the system continuously stabilizes the liquid inlet.
Example two
This embodiment provides a treatment system for a radioactive nuclear waste organic phase, as shown in fig. 2, comprising: the pretreatment unit, the wet catalytic oxidation treatment unit, the electrolytic oxidation treatment unit and the evaporation concentration treatment unit of the waste organic phase are sequentially connected. In particular, the method comprises the steps of,
the pretreatment unit comprises a liquid inlet system, a stirring system, a mixing system, a dosing system and the like. The liquid inlet system is composed of two parts of liquid inlet, one part is waste organic phase liquid inlet, and the waste organic phase liquid inlet pump 1 is used for feeding the waste organic phase liquid into the mixing system 5; the other part is evaporation concentration water production liquid, the evaporation concentration water production is diluent, and the two liquid phases enter a mixing system at the same time; since the waste organic phase belongs to an oil phase and is insoluble in water, an emulsifier needs to be added, and the emulsifier enters the mixing system through the emulsifier liquid inlet pump 2. After thorough mixing and stirring, a uniform diluted waste organic phase is formed in the mixing system (i.e., the mixing kettle). In the initial stage of system start-up, because evaporation concentration does not produce water, a certain amount of deionized water can be added during start-up, and evaporation concentration produces water can be directly introduced when evaporation concentration produces water, so that the system continuously stabilizes liquid inlet.
The wet catalytic oxidation treatment unit comprises a wet catalytic oxidation liquid inlet pump 6, a preheater 7, a reactor 8, a condenser 9, a gas-liquid separator 10, an air compressor 3, a steel cylinder buffer tank 4 and the like. The mixed uniform waste organic phase is mixed with high-pressure air discharged by an air compressor through a wet catalytic oxidation high-pressure liquid inlet pump (a high-pressure pump) and enters a wet catalytic oxidation unit for treatment. The wet catalytic oxidation reaction mechanism is as follows: under the conditions of high temperature, high pressure and catalyst, oxygen in the air is catalyzed to generate hydroxyl free radicals with stronger oxidizing capability under the condition of gas-liquid mixing, so that organic matters in a liquid phase are oxidized into carbon dioxide and water, and the wet catalytic oxidation treatment is mainly used for removing high-concentration organic matters. Firstly, the gas-liquid mixture is heated by a preheater, and then enters a reactor filled with a special catalyst, and COD in the waste organic phase is primarily treated cr Degradation is performed because of degradation of COD cr The heat is released, so that the reacted gas-liquid mixture carries heat to flow through the preheater to heat the feed liquid, and the redundant heat is taken away by circulating cooling water after passing through the condenser and enters a plant pipe network. Then, the cooled gas-liquid mixture is separated by a gas-liquid separator, because the wet catalytic oxidation process is to remove COD cr Degradation into water and carbon dioxide; therefore, the product gas is vented with excess air and the liquid enters the buffer tank 11. The selected wet catalytic oxidation high-pressure liquid inlet pump is a reciprocating or plunger type booster pump and has a metering function; the raw material components of the special catalyst in the reactor comprise a carrier, an active component and an auxiliary agent; the carrier of the catalyst is preferably anatase titanium dioxide; the active component is preferably a noble metal, more preferablyRuthenium and/or platinum; the auxiliary agent is preferably a rare earth element, more preferably cerium and/or lanthanum; an outlet of the gas-liquid separator adopts an automatic pneumatic needle valve, and the gas-liquid separator is made of stainless steel or more; the preheater is an energy recoverer, is in a shell-and-tube electric heating mode, and is made of stainless steel or more.
The electrolytic oxidation treatment unit includes a water intake system, a water discharge system, a reaction tank 13, an electrode 14, a circulation pump 15, and the like. After the waste organic phase passes through the wet catalytic oxidation treatment unit, COD (chemical oxygen demand) of the waste organic phase is obtained cr Has been degraded by 50-85%, most of the organics have been degraded or some macromolecules have been oxidized into small molecules. After the wet catalytic oxidation produced water passes through the buffer tank 11, the water directly enters the reaction tank for advanced oxidation treatment by the electrolytic oxidation liquid inlet pump 12, and the residual COD is degraded cr . The electrode is preferably a diamond electrode, and the material of the diamond electrode is preferably boron-doped diamond coated on the surface of the metal niobium; the electrode equipment is preferably the same in material and form of positive and negative electrode plates and is used for realizing instant mutual automatic switching of the positive electrode and the negative electrode by changing current. In the electrolysis process, the anode and the cathode of the electrode are changed through the current converter, so that the conversion between the anode and the cathode is realized, and scaling and ion deposition caused by long-time running of the electrode plate can be effectively avoided. The electrolytic oxidation mechanism is as follows: in the electrolytic process, hydroxyl radicals are generated on the surface of the electrode to degrade organic matters in the wastewater, and finally the organic matters are oxidized into inorganic matters, namely water and carbon dioxide. Electrolytic oxidation is mainly applied to COD with relatively low concentration cr Is removed. The waste organic phase after electrolytic oxidation treatment is basically completely degraded, and effluent COD cr Reaching the industrial sewage discharge standard or being undetectable.
Specifically, due to the limited electrode area, when the wastewater flows through the surface of the electrode, only part of the organic matters can contact the electrode, namely, part of the organic matters are oxidized; therefore, the whole COD in the wastewater is finally treated by multiple times of circulation cr And (5) degrading. In order to ensure that the whole process system has continuity, the electrolytic oxidation unit is provided with three sets of electrolytic oxidation reaction tanks, and each tank is provided with an electrode and a circulating pump; as shown in FIG. 2, the reaction tank 13 is a first reaction tank 13-1, a second reaction tank 13-2 and a third reaction tank 13-3 connected in parallel, the first reaction tank13-1 is provided with a first electrode 14-1 and a first circulation pump 15-1, a second reaction tank 13-2 is provided with a second electrode 14-2 and a second circulation pump 15-2, and a third reaction tank 13-3 is provided with a third electrode 14-3 and a third circulation pump 15-3; during normal operation, one reaction tank is filled with water, one reaction tank is subjected to cyclic electrolysis, one reaction tank is drained, automatic switching is realized among the three reaction tanks through a control system, and the continuity of overall water inlet and outlet is ensured. Wherein the volume of the buffer tank is the sum of the volumes of the three reaction tanks.
The evaporative concentration processing unit comprises a first mixing and stirring sedimentation tank 17, a second mixing and stirring sedimentation tank 18, a low-temperature evaporative concentration system 19 and the like. The water after electrolytic oxidation treatment enters a first mixing and stirring precipitation tank through an electrolytic oxidation liquid outlet pump 16, corresponding remover quicklime is added through phosphate ions detected on line, the addition amount of the quicklime is determined according to the content of phosphate radicals detected on line, the phosphate radicals react with the remover quicklime to generate phosphate precipitates, and further, the removal of the phosphate radicals is realized, and the generated phosphate is recovered. The waste water after phosphate radical removal enters a second mixing and stirring precipitation tank, and a certain amount of alkaline solution is added into the solution, wherein the alkaline solution is preferably ammonia water, and the ammonia water and uranyl nitrate in the waste water can be correspondingly precipitated as heavy oil acid salt. After precipitation and filtration, the heavy oil acid salt can be directly returned to a uranium purification and conversion workshop for effective recycling and utilization of uranium. The supernatant after precipitation mainly contains nitrate ions and alkaline solution cations, so that the supernatant enters a low-temperature evaporation concentration system for evaporation concentration and crystallization, and the produced water is relatively clean deionized water; part of the nitrate is discharged, and the other part of the nitrate returns to the front-end mixing and stirring tank, and the nitrate crystallized after evaporation and concentration is effectively recovered.
Specifically, the low-temperature evaporation concentration system comprises a concentrated water circulation system, a clear water circulation system, a brine circulation system, a wind circulation system, a heat pump circulation system and the like; the evaporating chamber and the condensing chamber are made of glass fiber reinforced plastic, the heat pump unit is a lithium bromide absorption heat pump, and the evaporating temperature is not higher than 70 ℃. The main principle of the low-temperature evaporation concentration system is to utilize the difference of the water content of saturated humid air under different temperature conditions to carry out evaporation separation (figure 3), and the corresponding saturated steam partial pressure is shown in figure 4. By heating and cooling the air, a certain amount of water vapor is continuously absorbed and released under the pushing of saturated vapor pressure, so that the evaporation and crystallization of the strong brine are realized. Meanwhile, in order to reduce energy consumption and running cost, the invention also introduces a heat pump unit, namely, the heat pump unit is used for heating the original strong brine by recovering latent heat released by condensing water vapor, and theoretically, the heat pump unit does not provide energy, but has energy loss in practice, and then, the heat pump unit supplements little energy, thus, the energy consumption can be greatly reduced, and the heat utilization rate is improved. Through dense water circulation system, clear water circulation system, salt water circulation system, wind circulation system and heat pump circulation etc. evaporation chamber and condensation chamber etc. are mutually cooperated and are used together and then realize the recovery to ammonium nitrate, and the clear water that produces can be discharged or get back to pretreatment unit and recycle.
In addition, the radioactive waste organic phase is treated by using the treatment system for radioactive waste organic phase shown in fig. 2, and the following examples are specifically set:
example III
This example provides a method for treating a radioactive nuclear waste organic phase, COD, of the waste organic phase cr About 130 ten thousand or so, comprising the steps of:
s1: firstly, the waste organic phase enters a pretreatment unit, the waste organic phase is mixed and diluted in a mixing system through a water inlet pump and water produced by an evaporation concentration unit according to a certain proportion, and meanwhile, a certain amount of emulsifying agent is added into the mixing system, and the waste organic phase is completely mixed and emulsified under the stirring state, so that the waste organic phase is formed. Wherein, the addition of the emulsifier is 2% of the mass of the waste organic phase, the stirring speed is 250rpm, and the liquid inlet ratio of the waste organic phase to the water is 1:40.
s2: the uniform waste organic phase enters a wet catalytic oxidation system through a wet catalytic oxidation high-pressure liquid inlet pump and air discharged by an air compressor, and sequentially enters a preheater, a reactor, a condenser and a gas-liquid separator, and carbon dioxide, nitrogen and the like generated after the reaction are directly discharged. The produced water enters a storage tank for entering the next processing unit. The conditions of the catalytic oxidation reaction specifically include: the pressure was 9MPa, the temperature was 270℃and the time was 2h. The raw material components of the catalyst comprise an anatase type titanium dioxide carrier, active component ruthenium and auxiliary agent cerium.
S3: the water produced by wet catalytic oxidation is sent into an electrolytic oxidation treatment unit for further advanced treatment by an electrolytic oxidation liquid inlet pump, so as to remove the corresponding residual COD cr . The electrolytic oxidation unit consists of three sets of electrode oxidation devices connected in parallel, can realize continuous water inlet and continuous water outlet, and has COD (chemical oxygen demand) of waste organic phase after electrolytic treatment cr The removal rate completely meets the national sewage discharge standard requirement. Wherein the electrolytic oxidation condition is a constant current condition, and the electrolytic current is 1000A; the electrolysis time was 4h.
S4: the water after the electrolytic treatment contains a small amount of phosphate ions, uranium and nitrate ions. Firstly, adding quicklime into a first mixing and stirring precipitation tank, removing phosphate radicals, and recycling generated calcium phosphate; adding ammonia water into the second mixing and stirring precipitation tank until the pH value is neutral, recovering uranium in the water phase, and returning the generated ammonium diuranate precipitate to a uranium purification and conversion process section for recycling; and thirdly, pumping the produced water containing ammonium nitrate into a low-temperature evaporation concentration system for evaporation concentration crystallization, and recovering ammonium nitrate. The produced water is neutral, one part of the produced water is discharged, and the other part of the produced water returns to the mixing system of the pretreatment unit to dilute the original waste organic phase for recycling.
Example IV
This example provides a method for treating a radioactive nuclear waste organic phase, COD, of the waste organic phase cr About 130 ten thousand or so, comprising the steps of:
s1: firstly, the waste organic phase enters a pretreatment unit, the waste organic phase is mixed and diluted in a mixing tank through a water inlet pump and water produced by an evaporation concentration unit according to a certain proportion, and meanwhile, a certain amount of emulsifying agent is added into the mixing tank, and the waste organic phase is completely mixed and emulsified under the stirring state, so that the waste organic phase is formed. Wherein, the addition of the emulsifier is 2% of the mass of the waste organic phase, the stirring speed is 250rpm, and the liquid inlet ratio of the waste organic phase to the water is 1:40.
s2: the uniform waste organic phase enters a wet catalytic oxidation system through a wet catalytic oxidation high-pressure liquid inlet pump and air discharged by an air compressor, and sequentially enters a preheater, a reactor, a condenser and a gas-liquid separator, and carbon dioxide, nitrogen and the like generated after the reaction are directly discharged. The produced water enters a storage tank for entering the next processing unit. The conditions of the catalytic oxidation reaction specifically include: the pressure is 7MPa, the temperature is 250 ℃ and the time is 2h. The raw material components of the catalyst comprise an anatase type titanium dioxide carrier, active component ruthenium and auxiliary agent cerium.
S3: the water produced by wet catalytic oxidation is sent into an electrolytic oxidation treatment unit for further advanced treatment by an electrolytic oxidation liquid inlet pump, so as to remove the corresponding residual COD cr . The electrolytic oxidation unit consists of three sets of electrode oxidation devices connected in parallel, can realize continuous water inlet and continuous water outlet, and has COD (chemical oxygen demand) of waste organic phase after electrolytic treatment cr The removal rate completely meets the national sewage discharge standard requirement. Wherein the electrolytic oxidation condition is a constant current condition, and the electrolytic current is 100A; the electrolysis time was 1h.
S4: the water after the electrolytic treatment contains a small amount of phosphate ions, uranium and nitrate ions. Firstly, adding quicklime into a first mixing and stirring precipitation tank, removing phosphate radicals, and recycling generated calcium phosphate; adding ammonia water into the second mixing and stirring precipitation tank until the pH value is neutral, recovering uranium in the water phase, and returning the generated ammonium diuranate precipitate to a uranium purification and conversion process section for recycling; and thirdly, pumping the produced water containing ammonium nitrate into a low-temperature evaporation concentration system for evaporation concentration crystallization, and recovering ammonium nitrate. The produced water is neutral, one part of the produced water is discharged, and the other part of the produced water returns to the mixing system of the pretreatment unit to dilute the original waste organic phase for recycling.
Further, for the third and fourth embodiments, index data of different sites of the processing system (see fig. 2 for each site position) is monitored, specifically as shown in tables 1 and 2, thereby monitoring COD cr And uranium content.
Table 1 index data for different loci in example III
Table 2 index data for different sites in example IV
From the table data it can be seen that: the treatment process of the waste organic phase has lower energy consumption and thorough treatment, successfully realizes the phase change of oil into water phase, and simultaneously does not produce secondary pollution in the treatment process, thereby achieving the recovery and reutilization of uranium.
Of course, other conditions and parameters in the process are also possible in addition to those exemplified in examples one to four.
The radioactive nuclear waste organic phase treatment system provided by the invention has the advantages of high equipment degree, mature technology of each section, low energy consumption, thorough treatment of the waste organic phase and the like, and can successfully realize the change of an oil phase into a water phase; meanwhile, the invention does not produce secondary pollution in the treatment process, can realize the recovery and reutilization of uranium, and effectively solves the technical problems which are not solved for many years in the nuclear industry and the potential safety hazard caused by long-term storage of waste organic phase.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "plurality" is two or more unless specifically defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (8)
1. A system for the treatment of a radioactive spent organic phase, comprising: the device comprises a pretreatment unit, a wet catalytic oxidation unit and an electrolytic oxidation unit;
wherein the pretreatment unit, the wet catalytic oxidation treatment unit and the electrolytic oxidation treatment unit are sequentially connected; the pretreatment unit is used for diluting the waste organic phase to obtain a uniform waste organic phase; the wet catalytic oxidation treatment unit is used for carrying out oxidation reaction on the uniform waste organic phase so as to primarily degrade COD in the waste organic phase cr Obtaining catalytic oxidation wastewater; the electrolytic oxidation treatment unit is used for further removing COD in the catalytic oxidation wastewater cr ；
The treatment system further comprises an evaporation concentration treatment unit; the evaporation concentration treatment unit is connected with the electrolytic oxidation treatment unit and is used for removing phosphate ions, uranium and nitrate ions in the electrolyzed water;
the pretreatment unit comprises a liquid inlet system, a mixing system and a dosing system; the mixing system is respectively connected with the liquid inlet system and the dosing system, and the dosing system is used for placing an emulsifying agent;
the wet catalytic oxidation treatment unit comprises a preheater, a reactor, a condenser and a gas-liquid separator which are connected in sequence;
wherein the preheater is used for preheating the uniform waste organic phase; the reactor is used for carrying out catalytic oxidation reaction on the preheated uniform waste organic phase; the gas-liquid separator is used for separating catalytic oxidation reaction products to obtain catalytic oxidation wastewater and gas-phase products;
the preheater is a shell-and-tube electric heater; the outlet of the gas-liquid separator adopts a pneumatic needle valve;
the electrolytic oxidation treatment unit comprises electrode equipment and a reaction tank; the electrode is a diamond electrode, and the diamond electrode is made of metal niobium, and the surface of the diamond electrode is coated with boron-doped diamond;
the positive and negative electrode plates of the electrode equipment are the same in material and form and are used for realizing instant mutual automatic switching of the positive electrode and the negative electrode by changing current;
the reaction tanks are three parallel reaction tanks, wherein the reaction tanks are a first reaction tank, a second reaction tank and a third reaction tank which are connected in parallel, the first reaction tank is used for water inflow, the second reaction tank is used for circulating electrolysis, and the third reaction tank is used for water drainage;
the evaporation concentration treatment unit comprises a first dosing reaction system, a second dosing reaction system and an evaporation concentration system which are sequentially connected; the first chemical adding reaction system is used for removing phosphate radical in the water after the electrolytic treatment, the second chemical adding reaction system is used for removing uranium in the water after the electrolytic treatment, and the evaporation concentration system is used for removing ammonium nitrate in the water after the electrolytic treatment;
a water outlet is formed in the evaporation concentration system and is connected with a liquid inlet system of the pretreatment unit through a pipeline;
the evaporation concentration treatment unit adopts a low-temperature evaporation concentration system, and the temperature of the low-temperature evaporation concentration system is not more than 70 ℃.
2. A method for treating a radioactive spent organic phase, characterized by using the treatment system according to claim 1, comprising the steps of:
s1: the waste organic phase enters a pretreatment unit, and is uniformly stirred with water and an emulsifying agent in a mixing system to form a uniform waste organic phase;
s2: the uniform waste organic phase enters a wet catalytic oxidation treatment system, is preheated and then undergoes catalytic oxidation reaction in a reactor, and then the reaction product is treated by a gas-liquid separator to respectively obtain catalytic oxidation wastewater and a gas-phase product;
s3: the catalytic oxidation wastewater enters an electrolytic oxidation treatment unit to further remove the residual COD in the wastewater cr Obtaining water after electrolytic treatment;
the step S3 further includes a step S4: the water after the electrolytic treatment enters an evaporation concentration treatment unit, phosphate ions, uranium and nitrate ions in the water after the electrolytic treatment are recovered in sequence, and a product water phase is finally obtained;
in the step S1:
the adding amount of the emulsifier is 2-5% of the mass of the waste organic phase, the stirring rotating speed is 150-250 rpm, and the liquid inlet ratio of the waste organic phase to water is 1: 20-1: 40, a step of performing a;
the emulsifier is nonionic emulsifier;
in the step S2:
the conditions of the catalytic oxidation reaction specifically include: the pressure is 5-9 MPa, the temperature is 250-270 ℃ and the time is 1-2 h;
in the step S3:
the electrolytic oxidation condition is a constant current condition, the electrolytic current is 100-1000A, and the electrolytic time is 4-8 h;
in the step S4:
adding quick lime into the first dosing stirring reaction system to remove phosphate radicals, and recycling generated calcium phosphate;
adding an alkaline solution into the second dosing stirring reaction system to obtain ammonium diuranate precipitate and produced water containing ammonium nitrate, and returning the generated ammonium diuranate precipitate to a uranium purification and conversion process section for recycling; feeding the produced water containing ammonium nitrate into a low-temperature evaporation concentration system for evaporation concentration and crystallization to obtain ammonium nitrate and evaporated concentrated produced water;
recovering ammonium nitrate, discharging one part of the evaporated and concentrated produced water, and returning the other part of the evaporated and concentrated produced water to a liquid inlet system of the pretreatment unit;
in the second dosing stirring reaction system, ammonia water is selected as the alkaline solution, and the ammonia water is added until the pH value of the online monitoring solution is equal to 7; the temperature of the low-temperature evaporation concentration system is not higher than 70 ℃.
3. The method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that:
in the step S1:
the adding amount of the emulsifier is 2% of the mass of the waste organic phase; the stirring speed is 250rpm; the liquid inlet ratio of the waste organic phase to the water is 1:40.
4. the method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that:
in the step S1:
the emulsifier is selected from ethylene oxide adducts of sorbitan fatty acid esters.
5. The method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that: the emulsifier is one or more of Tween 20, tween 60 and Tween 80.
6. The method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that:
in the step S2:
the conditions of the catalytic oxidation reaction specifically include: the pressure is 9MPa; the temperature is 270 ℃; the time was 2h.
7. The method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that:
in the step S2:
the raw material components of the catalyst comprise a carrier, an active component and an auxiliary agent; the carrier of the catalyst is anatase type titanium dioxide; the active component is noble metal, and the noble metal is ruthenium and/or platinum; the auxiliary agent is rare earth elements, and the rare earth elements are cerium and/or lanthanum.
8. The method for treating a radioactive nuclear waste organic phase according to claim 2, characterized in that:
in the step S3:
the electrolytic oxidation condition is a constant current condition, and the electrolytic current is 1000A; the electrolysis time was 4h.
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