CN103474123B - A kind of nanometer Fe/Mn composite catalyst is used for the method for radioactive spent resin oxygenolysis - Google Patents
A kind of nanometer Fe/Mn composite catalyst is used for the method for radioactive spent resin oxygenolysis Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 208000016261 weight loss Diseases 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 150000001455 metallic ions Chemical class 0.000 claims description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- -1 hydroxyl radical free radical Chemical class 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000004568 cement Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the method that a kind of nanometer Fe/Mn composite catalyst belonging to nuclear industry Radwastes treatment technical field is used for radioactive spent resin oxygenolysis.Method of the present invention adopts coprecipitation by NaOH and FeSO
47H
2o and MnSO
4h
2synthesis of nano Fe/Mn composite catalyst after O solution reaction; Then with nanometer Fe/Mn for catalyzer, by nanometer Fe/Mn and H
2o
2coupling produces OH, oxygenolysis mixing spent resin at temperature of reaction is 80 ~ 99 DEG C.Materials synthesis technique of the present invention is simple, and equipment requirement is low, and cost is low; Efficiently quick in order to process radioactive spent resin, reaction conditions is gentle, complete decomposition and non-secondary pollution, subtracts to hold effective, and economic security, has larger application prospect.
Description
Technical field
The invention belongs to nuclear industry Radwastes treatment technical field, be specifically related to the method that a kind of nanometer Fe/Mn composite catalyst is used for radioactive spent resin oxygenolysis.
Background technology
Radioactive spent resin produces primarily of places such as nuclear power station, nuclear fuel recovery place, comprises Zeo-karb and anion exchange resins.Resin used is the Nuclear grade resin of styrene-divinylbenzene type, has that exchange capacity is large, a little and radiotolerant feature of high, the homogeneous grain diameter of rate transition, solubleness in the hot water.In recent years, along with the fast development of nuclear industry and Nuclear Electricity, the radioactive spent resin produced by various nuclear facilities also grows with each passing day, and carries out the traffic expense needed for stabilization processes and final disposal and dispose expense also will be more and more higher to it.Therefore, how safety economy processes effectively is disposed growing radioactive spent resin, and the development for nuclear industry and Nuclear Electricity has very important significance.
The disposal route of radioactive spent resin general is at present included in certain inert base and forms stable firming body for solidification, the spent resin be about to containing radioactive nuclide, and then is transported to disposal site and carries out final disposal.Operation is simple for solidification method, but cause increase-volume, as spent resin is after direct cement solidification, volume increasing is twice, and may spalling be there is and cause nucleic leaching rate relatively high in resin solidification body chance water, thus bring very large risk to the safe disposal of refuse, increase the expense that postorder process is disposed.In order to reduce the solidification volume of refuse, obtaining and higher subtracting appearance coefficient, the subtracting of the spent resins such as burning, pyrolysis, acidolysis, high-temperature wet-oxidation is held technique and is developed.But these techniques all also exist temperature of reaction high, easily produce the shortcomings such as radioactive emission, equipment and operating cost are high.Wherein, wet raw noodles receives much concern.Be applied to the process of radioactive spent resin, the selection of catalyzer is crucial.Research shows, suitably uses catalyzer can greatly reduce temperature of reaction and pressure, makes its commercial Application become possibility.Catalyzer at present for catalytic wet oxidation reaction mainly contains: the precious metal being representative with Pt, Ru etc. take Cu as the transition metal oxide class of representative, with CeO
2for the rare-earth oxide class of representative.There are some researches show, the synergy between various metals can improve catalytic activity, as Mn/Ce compound demonstrates active and stability preferably to wet oxidation imidacloprid pesticide wastewater.
Summary of the invention
A kind of nanometer Fe/Mn composite catalyst is the object of the present invention is to provide to be used for the method for radioactive spent resin oxygenolysis.
A kind of nanometer Fe/Mn composite catalyst is used for the method for radioactive spent resin oxygenolysis, and concrete steps are as follows:
(1) by FeSO
47H
2o and MnSO
4h
2the solution of O presses metallic ion mol ratio 1:3 ~ 3:1 mix and blend, and passes into argon gas reaction is carried out under anaerobic state;
(2) in above-mentioned solution, NaOH solution is instilled, under room temperature, reaction generates nanometer Fe/Mn compound, blasting argon gas in course of reaction keeps reaction to carry out under anaerobic state, stirring is kept to react, by the nanometer Fe of synthesis/Mn particle precipitation, washing also obtains nanometer Fe/Mn composite catalyst after vacuum drying;
(3) by spent resin swelling and adjust ph in citric acid, then add nanometer Fe/Mn composite catalyst and stir, temperature of reaction is 80 ~ 99 DEG C, then instills H
2o
2, by nanometer Fe/Mn and H
2o
2the OH that reaction produces is by spent resin oxygenolysis.
Fe in step (2)
2+with OH in NaOH solution
-the ratio of amount of substance is 1:10 ~ 1:20.
Described in step (2), the time of reaction is 1 ~ 2h.
Spent resin described in step (3) is the granular wet resin of core level of styrene-divinylbenzene type, and water percentage is 40 ~ 60%, comprises Zeo-karb and anion exchange resins, containing radioactive nuclide.
Described in step (3), pH value is 2.0 ~ 3.0.
In step (3), the consumption of nanometer Fe/Mn composite catalyst counts 0.05 ~ 0.5g/g by the dry spent resin of unit;
H described in step (3)
2o
2for 30%(vol) H
2o
2solution, its consumption counts 10 ~ 60mL/g by the dry spent resin of unit.
The gas produced in spent resin processing procedure can directly discharge after condensing reflux, and condensed fluid is mainly small molecular organic acid and water, and the raffinate in reactor is curable disposal after treatment.
Nanometer Fe/Mn composite catalyst and H
2o
2reaction produces OH:
The Fe that nanometer Fe/Mn surface produces
2+and Mn
2+with H
2o
2fenton reaction occurs and produces hydroxyl radical free radical (OH), represent transition metal ion Fe and Mn with symbol M, formula (1) is shown in reaction.Cause a series of chain type oxidation reaction subsequently, produce the free radical OOH that oxidisability is poor, make Fe
2+and Mn
2+regeneration, formula (2 and 3).In course of reaction, there are some subsidiary reactions simultaneously, see formula (4 ~ 9).Namely react after the OH produced in system contacts with spent resin, resin transfer is soluble linear polystyrene, carbon dioxide and water, and produces sulfate radical or ammonium root.After this linear polystyrene continues to be further oxided as carbon dioxide and water.
M
n++H
2O
2→M
(n+1)
++·OH+OH
-(1)
M
(n+1)
++H
2O
2→M
n++·OOH+H
+(2)
M
(n+1)
++·OOH→M
n++O
2+H
+(3)
M
n++·OH→M
(n+1)
++OH
-(4)
H
2O
2+·OH→H
2O+·OOH(5)
H
2O
2+·OOH→·OH+H
2O+O
2(6)
·OH+·OH→H
2O
2(7)
·OOH+·OH→H
2O+O
2(8)
·OOH+·OOH→H
2O
2+O
2(9)
Beneficial effect of the present invention is: nanometer Fe prepared by the present invention/Mn catalytic composite material synthesis technique is simple, and equipment requirement is low, and cost is low; Efficiently quick with its process radioactive spent resin, reaction conditions is gentle, and without the need to High Temperature High Pressure, thoroughly and non-secondary pollution, subtract and hold effective, economically feasible, has broad application prospects in places such as nuclear power station, nuclear fuel recovery place.Can with hydrogen peroxide (H
2o
2) react the very strong hydroxyl radical free radical (OH) of generation oxidisability, thus by spent resin oxidative degradation, reach the object subtracting appearanceization; Have the advantages such as operating conditions is simple, economical and effective, can reduce the solidification volume of spent resin, obtain and higher subtract appearance coefficient, the safe handling for active nucleus waste matter is disposed and is provided wide application prospect.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Coprecipitation prepares nanometer Fe/Mn composite catalyst, and step is as follows: in four mouthfuls of round-bottomed flasks, add the FeSO that metallic ion mol ratio is 1:3 ~ 3:1
47H
2o(0.01 ~ 0.03M) and MnSO
4h
2o solution (0.03 ~ 0.01M) 100mL, stirs and passes into argon gas and make it to be in anaerobic state; Be that the NaOH solution 100mL of 0.2M is instilled in four mouthfuls of round-bottomed flasks by variable valve by concentration, make it react generation nano particle; After reaction 2h, by the nano particle of synthesis precipitation, deionized water washing twice, vacuum drying i.e. obtained nanometer Fe/Mn composite catalyst.
By nanometer Fe/Mn composite catalyst and H
2o
2coupling process ion exchange resin, mixing spent resin is AmberliteIRN77 Zeo-karb and IRN78 anion exchange resins (Rohm & Haas company, 909 types, nucleon level) mix, weight ratio is 1:1, and treatment capacity is 20g, water percentage is 50%(wt), soaking swelling adjustment pH with citric acid is 2.2, and in reactor, add nanometer Fe/Mn composite catalyst, consumption is 0.2g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 90 ± 1 DEG C.30%(vol is dripped in reaction vessel) H
2o
2solution, reaction 1.5h consumption is 20mL/g (in dry spent resin).H
2o
2drip rear continuation stirring reaction 0.5h.Result is in table 1:
Table 1 nanometer Fe/Mn composite catalyst process mixing spent resin
| Fe and Mn mol ratio | Resin decomposition rate (%) | TOC clearance (%) | Weight-loss ratio (%) |
| 1:3 | 72 | 61 | 50 |
| 1:2 | 79 | 70 | 54 |
| 1:1 | 88 | 79 | 60 |
| 2:1 | 91 | 86 | 62 |
| 3:1 | 92 | 89 | 65 |
Detection method: resin adopts UV, visible light spectrophotometer (Lambda25, and high performance liquid chromatography (Agilent1200Series PerkinElmer), Agilent, USA) measure, TOC value adopts total organic carbon/total blood urea/nitrogen analyzer (MultiN/C2100TOC/TN, Jena, Germany) measure, weight adopts electronic balance (Shimadzu AUW320) to measure.
Table 1 result shows, in Fe and Mn molar ratio range (1:3 ~ 3:1), and nanometer Fe/Mn composite catalyst and H
2o
2coupling can the spent resin of oxidative degradation mixing quickly and efficiently, and after reaction 2h, resin decomposition rate reaches more than 70%, TOC clearance and reaches more than 60%, and weight-loss ratio reaches more than 50%.
Embodiment 2
The preparation process of nanometer Fe/Mn composite catalyst is with embodiment 1, FeSO
47H
2o and MnSO
4h
2the metallic ion mol ratio of O solution is 1:1.
By nanometer Fe/Mn composite catalyst and H
2o
2coupling process ion exchange resin, mixing spent resin is that IRN77 Zeo-karb and IRN78 anion exchange resins mix, weight ratio is 1:2 ~ 2:1, treatment capacity is 30g, water percentage is 60%(wt), be 3.0 with citric acid swelling adjustment pH, in reactor, add nanometer Fe/Mn composite catalyst, consumption is 0.25g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 98 ± 1 DEG C.30%(vol is dripped in reaction vessel) H
2o
2solution, reaction 1.5h, consumption is 12.5mL/g (in dry spent resin).H
2o
2drip rear continuation stirring reaction 0.5h.Result is in table 2:
Table 2 nanometer Fe/Mn composite catalyst process mixing spent resin
Detection method: with embodiment 1.
Table 2 result shows, nanometer Fe/Mn composite catalyst and H
2o
2the mixing spent resin of coupling to Different Weight ratio all has good treatment effect, and after reaction 2h, resin decomposition rate reaches more than 80%, TOC clearance and reaches more than 70%, and weight-loss ratio reaches more than 50%.
Embodiment 3
The preparation process of nanometer Fe/Mn composite catalyst is with embodiment 2.
By nanometer Fe/Mn composite catalyst and H
2o
2coupling process ion exchange resin, mixing spent resin is that IRN77 Zeo-karb and IRN78 anion exchange resins mix, weight ratio is 1:1, treatment capacity is 10g, water percentage is 40%(wt), be 2.0 with citric acid swelling adjustment pH, in reactor, add nanometer Fe/Mn composite catalyst, consumption is 0.5g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 97 ± 1 DEG C.30%(vol is dripped in reaction vessel) H
2o
2solution, consumption is 60mL/g (in dry spent resin).Result is in table 3:
Table 3 nanometer Fe/Mn composite catalyst process mixing spent resin
| Reaction time (h) | Resin decomposition rate (%) | TOC clearance (%) | Weight-loss ratio (%) |
| 0.5 | 41 | 24 | 19 |
| 1.0 | 76 | 45 | 37 |
| 1.5 | 100 | 66 | 49 |
| 2.0 | 100 | 89 | 63 |
| 2.5 | 100 | 95 | 69 |
Detection method: with embodiment 1.
Table 3 result shows, nanometer Fe/Mn composite catalyst and H
2o
2coupling efficiently fast processing can mix spent resin, and after reaction 2.5h, resin decomposition rate reaches 100%, TOC clearance and reaches 95%, and weight-loss ratio reaches 69%.
Embodiment 4
The preparation process of nanometer Fe/Mn composite catalyst is with embodiment 2.
By nanometer Fe/Mn composite catalyst and H
2o
2coupling process, containing the simulated radioactive spent resins of caesium, be 1:1 water percentage is 50%(wt by 20g weight ratio) hybrid resin at the 20mLCs of 10mg/L
+24h is soaked in solution.Be 2.5 with citric acid swelling adjustment pH, in reactor, add nanometer Fe/Mn composite catalyst, consumption is 0.15g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 95 ± 1 DEG C; 30%(vol is dripped in reaction vessel) H
2o
2solution, reaction 2h consumption is 10mL/g (in dry spent resin), and result is in table 4:
Table 4 is containing the simulated radioactive spent resins processing procedure of caesium
Detection method: Cs
+concentration adopts atomic absorption spectrophotometer (AAS) (AAS6VARIO) to measure.
Table 4 result shows, simulated radioactive spent resins is through nanometer Fe/Mn composite catalyst and H
2o
2after coupling process, the Cs entrained by it
+the overwhelming majority is all trapped in decomposes in raffinate and residue, only has the Cs of denier
+may go out with the entrainment produced in course of reaction, condense in again in condensed fluid after condensation, not containing Cs in final gas of discharging
+, condensed fluid can process rear discharge, raffinate and residue curable disposal after concentrated.The method substantially reduces the volume of spent resin, has saved the storage of refuse, transport and disposal costs, has the advantages such as operation is simple, easy control and management, demonstrates larger using value.
Claims (7)
1. nanometer Fe/Mn composite catalyst is used for a method for radioactive spent resin oxygenolysis, and it is characterized in that, concrete steps are as follows:
(1) by FeSO
47H
2o and MnSO
4h
2the solution of O presses metallic ion mol ratio 1:3 ~ 3:1 mix and blend, and passes into argon gas reaction is carried out under anaerobic state;
(2) in above-mentioned solution, NaOH solution is instilled, under room temperature, reaction generates nanometer Fe/Mn compound, blasting argon gas in course of reaction keeps reaction to carry out under anaerobic state, stirring is kept to react, by the nanometer Fe of synthesis/Mn particle precipitation, washing also obtains nanometer Fe/Mn composite catalyst after vacuum drying;
(3) by spent resin swelling and adjust ph in citric acid, then add nanometer Fe/Mn composite catalyst and stir, temperature of reaction is 80 ~ 99 DEG C, then instills H
2o
2, by nanometer Fe/Mn and H
2o
2the OH that reaction produces is by spent resin oxygenolysis;
Spent resin resolution ratio reaches 70-100%, and TOC clearance reaches more than 60%, and weight-loss ratio reaches more than 50%.
2. method according to claim 1, is characterized in that, Fe in step (2)
2+with OH in NaOH solution
-the ratio of amount of substance is 1:10 ~ 1:20.
3. method according to claim 1, is characterized in that, described in step (2), the time of reaction is 1 ~ 2h.
4. method according to claim 1, it is characterized in that, spent resin described in step (3) is the granular wet resin of core level of styrene-divinylbenzene type, and water percentage is 40 ~ 60%, comprise Zeo-karb and anion exchange resins, containing radioactive nuclide.
5. method according to claim 1, is characterized in that, described in step (3), pH value is 2.0 ~ 3.0.
6. method according to claim 1, is characterized in that, in step (3), the consumption of nanometer Fe/Mn composite catalyst counts 0.05 ~ 0.5g/g by the dry spent resin of unit.
7. method according to claim 1, is characterized in that, H described in step (3)
2o
2be the H of 30% (vol)
2o
2solution, its consumption counts 10 ~ 60mL/g by the dry spent resin of unit.
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|---|---|---|---|
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| UA117984C2 (en) * | 2014-11-19 | 2018-10-25 | Фраматоме Гмбх | Method and apparatus for the recovery of radioactive nuclides from spent resin materials |
| CN109961867B (en) * | 2019-03-27 | 2021-04-06 | 华中科技大学 | Method for treating radioactive mixed ion exchange resin by Fenton-like oxidation method |
| CN110759561A (en) * | 2019-10-23 | 2020-02-07 | 江苏中海华核环保有限公司 | Waste resin Fenton oxidation device and oxidation method thereof |
| CN113096843B (en) * | 2019-12-23 | 2024-04-23 | 中广核研究院有限公司 | Method for treating radioactive solid waste |
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| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
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| Fenton试剂催化氧化法处理离子交换树脂再生废水;车春波;《环境科学与管理》;20100228;第35卷(第2期);全文 * |
| Miia Vilve et al..Degradation of 1,2-dichloroethane from wash water of ion-exchange resin using Fenton"s oxidation.《Environ Sci Pollut Res》.2010,第17卷全文. * |
| T.L Gunale et al..Studies in liquid phase mineralization of cation exchange resin by a hybrid process of Fenton dissolution followed by wet oxidation.《Chemical Engineering Journal》.2009,第148卷全文. * |
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