CN103474123A - Method of using nano Fe/Mn composite catalyst for oxidative decomposition of radioactive waste resin - Google Patents
Method of using nano Fe/Mn composite catalyst for oxidative decomposition of radioactive waste resin Download PDFInfo
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- CN103474123A CN103474123A CN201310373029XA CN201310373029A CN103474123A CN 103474123 A CN103474123 A CN 103474123A CN 201310373029X A CN201310373029X A CN 201310373029XA CN 201310373029 A CN201310373029 A CN 201310373029A CN 103474123 A CN103474123 A CN 103474123A
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- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002901 radioactive waste Substances 0.000 title abstract description 5
- 238000006864 oxidative decomposition reaction Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 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
- 230000002285 radioactive effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture 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
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 abstract 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 abstract 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract 1
- 239000010812 mixed waste Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 230000008878 coupling Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 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
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 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
- 230000018109 developmental process Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation 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
- 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
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010914 pesticide waste 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of radioactive waste treatment in the nuclear industry, and discloses a method of using nano Fe/Mn composite catalyst for oxidative decomposition of radioactive waste resin. The method includes firstly, subjecting NaOH and a FeSO4.7H2O and MnSO4.H20 solution to reaction by a coprecipitation method prior to synthesizing a nano Fe/Mn composite catalyst; secondly, taking nona Fe/Mn as a catalyst to combine the nona Fe/Mn with H2O2 to generate .OH, and subjecting mixed waste resin to oxidative decomposition at the reaction temperature of 80-99 DEG C. The method is simple in material synthesis technology, low in equipment requirement and low in cost, is efficient and rapid when used for treating the radioactive waste resin, mild in reaction conditions, complete in decomposition, free of secondary pollution, good in volume reduction effect, economical and safe, and has great application prospect.
Description
Technical field
The invention belongs to nuclear industry radioactive waste processing technology field, be specifically related to the method for a kind of nanometer Fe/Mn composite catalyst for the radioactive spent resin oxygenolysis.
Background technology
Radioactive spent resin is mainly produced by places such as nuclear power station, nuclear fuel recovery place, comprises Zeo-karb and anion exchange resins.The Nuclear grade resin that resin used is styrene-divinylbenzene type, have that exchange capacity is large, high, the homogeneous grain diameter of rate transition, the solubleness in hot water is little and radiotolerant feature.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 it is carried out stabilization processes and the required traffic expense of final disposal and disposes expense also will be more and more higher.Therefore, how safety economy is effectively processed and is disposed growing radioactive spent resin, for the development of nuclear industry and Nuclear Electricity, has very important significance.
At present the disposal route of general radioactive spent resin is for solidifying, and the spent resin that is about to contain radioactive nuclide is included in certain inert base and forms stable firming body, and then is transported to disposal site and carries out final disposal.Operation is simple for solidification method, but cause increase-volume, as increasing, spent resin volume through after direct cement solidification is twice, and spalling may occur and cause the nucleic leaching rate relatively high in resin solidification body chance water, thereby bring very large risk to the safe disposal of refuse, increase postorder and process the expense of disposing.In order to reduce the curing volume of refuse, obtain the higher appearance coefficient that subtracts, the subtracting of the spent resins such as burning, pyrolysis, acidolysis, high-temperature wet-oxidation held technique and is developed.But these techniques all exist temperature of reaction high, easily produce the shortcomings such as radioactive emission, equipment and operating cost height.Wherein, the catalytic wet oxidation technology receives much concern.Be applied to the processing 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.At present the catalyzer for the catalytic wet oxidation reaction mainly contains: take the precious metal that Pt, Ru etc. are representative, the transition metal oxide class that the Cu of take is representative, with CeO
2rare-earth oxide class for representative.There are some researches show, the synergy between various metals can improve catalytic activity, as the Mn/Ce compound demonstrates activity and stability preferably to wet oxidation imidacloprid pesticide waste water.
Summary of the invention
The object of the present invention is to provide the method for a kind of nanometer Fe/Mn composite catalyst for the radioactive spent resin oxygenolysis.
A kind of nanometer Fe/Mn composite catalyst is 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 is pressed metal ion mol ratio 1:3~3:1 mix and blend, and pass into argon gas make the reaction under anaerobic state, carry out;
(2) splash into NaOH solution in above-mentioned solution, under room temperature, reaction generates nanometer Fe/Mn compound, blasting argon gas in course of reaction keeps reaction to carry out under anaerobic state, keep stirring and reacted, by synthetic nanometer Fe/Mn particle precipitation, after washing vacuum drying, obtain nanometer Fe/Mn composite catalyst;
(3) by spent resin swelling regulate the pH value in citric acid, then add nanometer Fe/Mn composite catalyst to stir, temperature of reaction is 80~99 ℃, then splashes into H
2o
2, by nanometer Fe/Mn and H
2o
2the OH that reaction produces is by the 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.
The granular wet resin of core level that spent resin described in step (3) is styrene-divinylbenzene type, water percentage is 40~60%, comprises Zeo-karb and anion exchange resins, contains radioactive nuclide.
Described in step (3), the pH value is 2.0~3.0.
The consumption of nanometer Fe in step (3)/Mn composite catalyst is counted 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 is counted 10~60mL/g by the dry spent resin of unit.
The gas produced in the 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/the Mn surface produces
2+and Mn
2+with H
2o
2the Fenton reaction occurs and produce hydroxyl radical free radical (OH), with symbol M, represent transition metal ion Fe and Mn, formula (1) is shown in reaction.Cause subsequently a series of chain type oxidation reactions, produce the poor free radical OOH of oxidisability, make Fe
2+and Mn
2+regeneration, formula (2 and 3).In course of reaction, exist some subsidiary reactions simultaneously, see formula (4~9).The OH produced in system with react after spent resin contacts, resin is converted into water-soluble straight chain polystyrene, carbon dioxide and water, and produces sulfate radical or ammonium root.After this straight chain polystyrene continues to be further oxided into 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 composite catalyzing agent material synthesis technique is simple, and equipment requirement is low, and cost is low; Process radioactive spent resin with it efficiently quick, the reaction conditions gentleness, without High Temperature High Pressure, thorough and non-secondary pollution, subtract appearance effective, and economically feasible, have broad application prospects in places such as nuclear power station, nuclear fuel recovery place.Can with hydrogen peroxide (H
2o
2) the very strong hydroxyl radical free radical (OH) of reaction generation oxidisability, thereby by spent resin oxidative degradation, reach the purpose that subtracts appearanceization; There is the advantages such as operating conditions is simple, economical and effective, can reduce the curing volume of spent resin, obtain the higher appearance coefficient that subtracts, for the safe handling of active nucleus waste matter, dispose wide application prospect is provided.
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: add the FeSO that the metallic ion mol ratio is 1:3~3:1 in the four-hole round-bottomed flask
47H
2o(0.01~0.03M) and MnSO
4h
2o solution (0.03~0.01M) 100mL, stir and pass into argon gas and make it in anaerobic state; The NaOH solution 100mL that is 0.2M by concentration splashes in the four-hole round-bottomed flask by variable valve, makes its reaction generate nano particle; After reaction 2h, by synthetic nano particle precipitation, deionized water washing twice, vacuum drying makes nanometer Fe/Mn composite catalyst.
By nanometer Fe/Mn composite catalyst and H
2o
2ion exchange resin is processed in coupling, and mixing spent resin is Amberlite IRN77 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, and water percentage is 50%(wt), soaking swelling adjusting pH with citric acid is 2.2, adds nanometer Fe/Mn composite catalyst in reactor, and consumption is 0.2g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 90 ± 1 ℃.Drip 30%(vol 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 is processed and is mixed spent resin
Fe and Mn mol ratio | Resin resolution ratio (%) | 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, PerkinElmer) and high performance liquid chromatography (Agilent1200Series, Agilent, USA) measure, the TOC value adopts total organic carbon/total blood urea/nitrogen analyzer (MultiN/C2100TOC/TN, Jena, Germany) to 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 oxidative degradation mixing quickly and efficiently spent resin, after reaction 2h, the resin resolution ratio reaches more than 70%, and the TOC clearance 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
2ion exchange resin is processed in coupling, 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), regulating pH by the citric acid swelling is 3.0, adds nanometer Fe/Mn composite catalyst in reactor, and consumption is 0.25g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 98 ± 1 ℃.Drip 30%(vol 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 is processed and is mixed spent resin
Detection method: with embodiment 1.
Table 2 result shows, nanometer Fe/Mn composite catalyst and H
2o
2coupling all has treatment effect preferably to the mixing spent resin of Different Weight ratio, and after reaction 2h, the resin resolution ratio reaches more than 80%, and the TOC clearance 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
2ion exchange resin is processed in coupling, 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), regulating pH by the citric acid swelling is 2.0, adds nanometer Fe/Mn composite catalyst in reactor, and consumption is 0.5g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 97 ± 1 ℃.Drip 30%(vol 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 is processed and is mixed spent resin
Reaction time (h) | Resin resolution ratio (%) | 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 mixes spent resin, and after reaction 2.5h, the resin resolution ratio 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
2the simulated radioactive spent resins containing caesium is processed in coupling, by the 20g weight ratio, is that the 1:1 water percentage is 50%(wt) hybrid resin at the 20mL of 10mg/L Cs
+soak 24h in solution.Regulating pH by the citric acid swelling is 2.5, adds nanometer Fe/Mn composite catalyst in reactor, and consumption is 0.15g/g (in dry spent resin) simultaneously; Mechanical raking, temperature of reaction is 95 ± 1 ℃; Drip 30%(vol in reaction vessel) H
2o
2solution, reaction 2h consumption is 10mL/g (in dry spent resin), 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 is processed, the Cs that it is entrained
+the overwhelming majority all is 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 after condensation in condensed fluid, not contain Cs in final gas of discharging
+, condensed fluid can be processed rear discharge, the curable disposal after concentrated of raffinate and residue.The method has reduced the volume of spent resin greatly, has saved storage, transportation and the disposal costs of refuse, has the advantages such as operation is simple, easy control and management, demonstrates larger using value.
Claims (7)
1. nanometer Fe/Mn composite catalyst, for the method for radioactive spent resin oxygenolysis, is characterized in that, concrete steps are as follows:
(1) by FeSO
47H
2o and MnSO
4h
2the solution of O is pressed metal ion mol ratio 1:3~3:1 mix and blend, and pass into argon gas make the reaction under anaerobic state, carry out;
(2) splash into NaOH solution in above-mentioned solution, under room temperature, reaction generates nanometer Fe/Mn compound, blasting argon gas in course of reaction keeps reaction to carry out under anaerobic state, keep stirring and reacted, by synthetic nanometer Fe/Mn particle precipitation, after washing vacuum drying, obtain nanometer Fe/Mn composite catalyst;
(3) by spent resin swelling regulate the pH value in citric acid, then add nanometer Fe/Mn composite catalyst to stir, temperature of reaction is 80~99 ℃, then splashes into H
2o
2, by nanometer Fe/Mn and H
2o
2the OH that reaction produces is by the spent resin oxygenolysis.
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, the granular wet resin of core level that spent resin described in step (3) is styrene-divinylbenzene type, water percentage is 40~60%, comprise Zeo-karb and anion exchange resins, contain radioactive nuclide.
5. method according to claim 1, is characterized in that, described in step (3), the pH value is 2.0~3.0.
6. method according to claim 1, is characterized in that, the consumption of nanometer Fe in step (3)/Mn composite catalyst is counted 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
2for 30%(vol) H
2o
2solution, its consumption is counted 10~60mL/g by the dry spent resin of unit.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107004450A (en) * | 2014-11-19 | 2017-08-01 | 阿海珐有限公司 | Method and apparatus for reclaiming radionuclide from the resin material after |
CN109961867A (en) * | 2019-03-27 | 2019-07-02 | 华中科技大学 | Using the method for class Fenton oxidation method processing radioactivity mixture iron exchange resin |
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CN113096843A (en) * | 2019-12-23 | 2021-07-09 | 中广核研究院有限公司 | Method for treating radioactive solid waste |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107004450A (en) * | 2014-11-19 | 2017-08-01 | 阿海珐有限公司 | Method and apparatus for reclaiming radionuclide from the resin material after |
CN107004450B (en) * | 2014-11-19 | 2019-05-21 | 法玛通有限公司 | Method and apparatus for recycling radionuclide from the resin material after |
CN109961867A (en) * | 2019-03-27 | 2019-07-02 | 华中科技大学 | Using the method for class Fenton oxidation method processing radioactivity mixture iron exchange resin |
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 |
CN113096843A (en) * | 2019-12-23 | 2021-07-09 | 中广核研究院有限公司 | Method for treating radioactive solid waste |
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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