On extracting and application of noble metal fission product alloy particles from spent fuel as catalysts

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1 CIAE LOGO On extracting and application of noble metal fission product alloy particles from spent fuel as catalysts Daqing Cui Team: Y. Ouyang, S. Xiao, T. Li, L.Wang & G.Ye China Institute of Atomic Energy , IAEA Vienna

2 Content 1 2 Introduction FP alloy particles charaterization, composition, size & structure 3 Charaterization of catalytical effect & β radiation 4 As electrolysis catalysts 5 As photo catalysts 6 Optimizing FP noble metal extracting methods Company Logo

3 in the World SNP generated per year in China t/a SNP accumulated in China, t

4 Nuclear Fuel Cycle Options 1. Direct disposal 2. Monorecycling Pu 3. Multirecycling Pu 4. Multirecycling Pu & An 5. Improved option4 with separation of Cs, Sr 6. Transmutation of long lived fission products

5 The best cleaner is who can both clean the house and sell the waste at a good price

6 SNF

7 SNF U & Pu reprocessing Waste

8 SNF U & Pu reprocessing Waste Minor An Sr +Cs FP alloy Particles as H 2 catalysts

9 235 U + n 138 Ba + 95 Mo + 3n + 6β - : 7.8 x 10 7 KJ/g What are noble FP metals? 1/ How much will be created in a spent fuel? 2/ How will be their radio activities & toxicities? How to Separate and Utilize? a) Extracting FP noble metals from high level liquid Waste, by electro deposition M. Ozawa, JAEA as Electrode catalysts for H 2 production b) Directly extracting as original particles as catalysts for photocatalyst or electrolyse/fuel cell catalysts 2

10 Fission product yield from normal LWR 29%x6.5g/130g = 1.45% Particles / solid solution in UO2? RE, Y: 24% Mo,Ru, Tc, Rh, Pd: 29% Kr, Xe: 15% Zr, Nb: 14% Cs, Rb, I, Te: 11% Ba, Sr: 7%

11 11 Period 1 IA 1A Group** 1 H Li Na K Rb Cs Fr (223) 2 IIA 2A 4 Be Mg Ca Sr Ba Ra (226) Periodic Table of the Elements 3 IIIB 3B 21 Sc Y La* Ac~ (227) 4 IVB 4B 22 Ti Zr Hf Rf (257) 5 VB 5B 23 V Nb Ta Db (260) 6 VIB 6B 24 Cr Mo W Sg (263) 7 VIIB 7B 25 Mn Tc (98) 75 Re Bh (262) VIII Fe Ru Os Hs (265) 27 Co Rh Ir Mt (266) 28 Ni Pd Pt () 11 IB 1B 12 IIB 2B 13 IIIA 3A 5 B Al Cu Zn Ga Ag Cd In Au Hg Tl () () 14 IVA 4A 6 C Si Ge Sn Pb () 15 VA 5A 7 N P As Sb Bi VIA 6A 8 O S Se Te Po (210) () 17 VIIA 7A 9 F Cl Br I At (210) 18 VIIIA 8A 2 He Ne Ar Kr Xe Rn (222) () Classification (Kleykamp, 1975) 1) Dissolved in the matrix: Rb, Sr, Y, Zr, Nb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu 2) Partly precipitated at grain boundaries (oxides): Rb, Sr, Zr, Nb, Mo, Te, Cs, Ba 3) Metallic precipitates: Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te 4) Volatiles: Br, Kr, Rb, I, Xe, Cs Lanthanide Series* Actinide Series~ 58 Ce Th Pr Pa (231) 60 Nd U (238) 61 Pm (147) 93 Np (237) 62 Sm Pu (242) 63 Eu Am (243) 64 Gd Cm (247) 65 Tb Dy Ho Er Bk Cf Es (247) (249) (254) 100 Fm (253) 69 Tm Md (256) Yb Lu No (254) 103 Lr (257)

12 Mo-Ru-Tc-Pd-Rh FP alloy particles formed in nuclear fuel Particle size bigger in central part due to better diffusion at higher temrature. Contents differ due to Pu/U vary

13 Spent Fuel as Nuclear Ore Metal Se Mo Rh Pd Ag Te Richest ore Contents (ppm) (12~92) 140 (0.4~0.6) 2.4~7.4 46~201 (3.6~29) LWR Conc.(ppm) 50~98 4,021~6, ~949 1,900~4, ~ ~842 Ratio (-) , ,966 2,543 6, ,840 FBR Conc.(ppm) Ratio (-) ,652 1, Remark Estimated from Cu ore in Russia UGMK (2004) Results of Erdenet mine in Mongolia Estimate from PGM production results in main mine Results of North American palladium Ltd in Canada Results of Galmony mine in Ireland and Dikulushi mine in Congo Estimated from Cu ore in Russia UGMK (2004) The mass of NRM generated in SNF worldwide is similar with the total production, Rh is even more, 2.5 time higher National Demands of PGM in Japan (FY2006);Ru:3.7t, Rh:2.7t, Pd:50.6t Ozawa: In estimating nuclear fuel cycle capacity in Japan can cover ca.100% of Ru, ca.40% of Rh and ca.7% of Pd against the demands.

14 Repository NRM particles H2 catalyst

15 Previous work 1. D. Cui*, J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, , DOI: /C0EE00582G 2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf, D. J. Wronkiewicz and K. Spahiu, Charactorisation of alloy particles extracted from spent nuclear fuel, Journal of Nuclear Materials 420, 1-3 (2012) D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru- Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92( ) (2004) 5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001) 6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Manuscript to JNM, Company Logo

16 1. D. Cui*, J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, , DOI: /C0EE00582G 2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf, D. J. Wronkiewicz and K. Spahiu, Charactorisation of alloy particles extracted from spent nuclear fuel, Journal of Nuclear Materials 420, 1-3 (2012) D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru- Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92( ) (2004) 5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001) 6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Submitted to JNM, Company Logo

ppb Un Oxic extraction Normal Reprocessing, oxic HNO 3 oxidative corrosion of alloy particles Conditions: UO 2 soluble,but NRM alloy particles stable? Ru, Pd, Rh 0.5 ppb, Mo= 900ppb stabilized 1.

17 ppb Un Oxic extraction Normal Reprocessing, oxic HNO 3 oxidative corrosion of alloy particles Conditions: UO 2 soluble,but NRM alloy particles stable? Ru, Pd, Rh 0.5 ppb, Mo= 900ppb stabilized 1. Similar alloy without Tc 46Mo-29-Ru-21-Pd-4Rh. ~1800 o C melte, Aging in Ar, 1511 o C, 4 o C/min Test (6 g, 4 cm 2 /g) in 25 ml.under gental conditions in that UO 2 dissolved easily In deoxygenated H 3 PO o C Mo-100 Pd-105 Rh hours

18 BWR 23 MWd/KgU, rumped SNF Dissolving SNP in H 3 PO 4 at 113 o C (glass-fiber filter) Residue wash & dry filterate ICP-MS Testing as catalyst flashing Ar/Ar+10%H 2 H 2 - U(VI) Np(V) Pu(V) Se(IV) ph3 and ph8.5 vs. 合成合金, Fe(0) Charaterising -spectrometry XRD SEM-WDS TEM-EDS-diffraction EXAFS

19 SEM

20 SEM

21 TEM 5nm

22 TEM

23 50nm

$Rotation electron diffraction(red) Single$ Reciprocal space Zhang et al. Z. Kristallogr.

24 Rotation electron diffraction(red) Single crystal ED on nano-crystals Eward sphere Reciprocal space Zhang et al. Z. Kristallogr., 2010, 225, Wan, et al. J. Appl. Cryst., 2013, 46,

25 TEM - RED

$Scanning of XRD film, 0.5 mg alloy residue (*trace UO 2 ) Diffraction patterns from a 10 nm sized particle.$

26 Scanning of XRD film, 0.5 mg alloy residue (*trace UO 2 ) Diffraction patterns from a 10 nm sized particle. D(Å) calculated from distances XRD on alloy residue TEM-diffraction on a nanoparticle a, nm c, nm d(å) Intensity d(å) values measured , 2.09, 2.07, , , 2.24, 2.21, , 1.18, * 10 1) Residues nondestructicely, with hexagonal symmetry extracted from SF MoRuTcRhPaTe ) Tc element )Ru element , * * 5 4)synthesized Mo40Ru50Pd10 epsilon alloy phase[park 2000] Park et al Korean Chem. Soc. 2000, 21,

$7µm TEM-EDS analysis on nanoparticles Calculated inventories, 23 MWd/kgU Literature data for comparison TEM-diffraction 0.5-0.$

27 Characterization of metal alloy particles SEM-WDS on the biggest particles, µm TEM-EDS analysis on nanoparticles Calculated inventories, 23 MWd/kgU Literature data for comparison TEM-diffraction mm particles + clusters (composed by ~10 nm sized nanoparticles): TEM-EDS & SEM-WDS: similar sized particles have similar composition. nm particles outside cluster differ in composition fission products SEM_WDS average of 8 submicroparticles ± s Mo Ru Tc Pd Rh Te 32.7 ± ± ± ± ± ±1.4 TEM-EDS average of 9 clustered nanoparticles ± s 26,5 ± 4,4 32,7 ±5,4 7,6 ±3,0 23,1 ±3,0 6,3 ±3,9 4,9 ±3,4 nanoparticle analysed by TEM diffraction 23,2 38,9 4,26 19,2 7,49 6,85 particles from HNO 3 SF reprocessing calculated fission yield [Origen] normalized at.%

28 EXAFS of 4d-metal particles Particles extracted from spent fuel fine structure Fourier transform modulus Spectral edges (Mo, Tc and Ru). EXAFS: all elements are in similar conditions hemogenoius (true) alloy synthetic particles EXAFS : Mo in the residue is very well coordinated with other metals

29 Test NRM alloy particles: catalyst in 10 % H2 to reduce U(VI) Np(V) Pu(VI)? 25 ml 10NaCl 2mM NaHCO 3 solution with U(VI) Pu(VI), Np(V) Tc(VII) Se(VI), flashing Ar+0.03%CO 2 +10% H 2 mixture ph3 (non sorption) & ph8.5 Study the fates of nuclides in following batch test, 5.5 mg NRM particles 1 cm 2 similar synth alloy, but no Tc 1 cm 2 similar synth alloy, 0.1 mm source ( 90 Sr 370kBq) effects 1 cm 2 iron metal,disposal canister material

30 ppb Experiments at ph 3.0, 5%H2: U(VI), Pu(VI), Np(V) ppb 10000, , ,00 100,00 100,00 10,00 10,00 U 1,00 Pu 1,00 0,10 0,00 0,00 0,00 1,00 0,10 0,10 0,00 5,00 10,00 15,00 20,00 25,00 30,00 0,01 0,00 5,00 10,00 15,00 20,00 25,00 30,00 days day Np 0,01 0,00 5,00 10,00 15,00 20,00 25,00 30,00 days H 2 has no reducing effects Synt alloy has some effect Synt alloy + β much bigger effects Extracted alloy has highest effcts

31 β radioisotopes in FP alloy particles

32 Green energy, H 2 & fuel cell need catalysts H 2 from 4Gen. NPP Photolyzer, Photocatalysis calalysis Company Logo

33 Company Logo

34 Wind power is over built night day Hydrogen made by the electrolysis of water is now cost-competitive and gives us another building block for the low-carbon economy July 05, 2017, More competitive if the low cost high efficient radcatalysts can be developed.

35 Electro-deposition of NRM in S-HLLW; HCl vs. HNO 3 media (Masaki Ozawa) HNO3-S-HLLW HCl-S-HLLW Pd; must be higher Electrolysis; Catholyte: 50cm 3, 50, Cathode: Pt smooth, 2cm 2, Ic: 2.5mA/cm 2 (1hr) 75(2hr) 100(4hr), ICP Atomic Emission Spectrometry 16

36 Micro NRM Deposits by CEE of S-HLLW HCl-0.5M SEM/EDS Analysis Mixture of Dendrite and Coagulated fine sphere particles Metal ; Ru,Pd,Rh, Oxide ; ReO 3, TcO 2, MoO 2 Ru, Rh, Re > Pd, Mo by 17

37 Catalytic Activity of various NRM deposits for Electrolytic H 2 Production in 1M NaOH soln. S-HLLW-0.5M HCl S-HLLW-0.5M HNO 3 - Pd added S-HLLW-0.5M HNO H ad H + + e H + + e - H ad -0.8 Pd:Ru:Rh:Re=3.5:4:1:1 *1 Pd:Ru:Rh:Re=1:1:1:1 Pd:Ru:Rh:Re=3.5:4:1:1 *2 Pd Rh Pd-Ru Pd-Rh Pd-Re Ru-Rh CV on NRM-deposit Electrodes 19

38 Utilization of NRM-deposit Electrodes (Masaki Ozawa) 1) Highest catalytic reactivity has been assigned to the quaternary deposit (Pd-Ru-Rh- Re (3.5:4:1:1)) electrode, in electrolysis either in NaOH or artificial sea water (Global2007). 2) Noblest φh init. (>-1.05V) was observed on NRM deposit electrodes from S-HLLW (HCl, HNO 3 ) 3) Energy consumption of such electrodes on H 2 production was about half of smooth Pt electrode, specifically in artificial sea water (ibid.). 4) Those (including the deposit from S-HLLW) reactivity, better that of Pt-black electrode as well as smooth Pt (ibid.). 5) A high reactivity would attribute to higher numbers of Ru and Rh atoms at the surface (Global2007, 2009). Higher adsorption sites for H + by them was responsible. 6) Tc showed higher reactivity than that of Re, in/off the combination with Rh (ibid.) Due to its beta?

39 In reprocessing, FP alloy particles partly exist as residue in filters or filtrates called as black shit, often stop filter, or cause short cut during vatrification of HLW, deposite in glass. How to extract FP alloy particles? H2 produced 3G NPP, the electrolzse water to H2 +O2 during nights, high cost catalyst? H2 used by car or convert to electricity during the day. Sunshine photolyse water Radioactive (Mo-Ru-Tc-Pd-Rh) - TiO 2, combined photocatalyst Study the machenism, how much and why beta radioactivity can enhance the calalyst properties

40 3.2eV,λ<387nm ultra violet light

41 Alloy catalyst Rh:Pd combined effect? Company Logo

42 β accelerator β accelerator H 2 gas analysis Light Experimental set up

43 Some positive effects of beta radiation On redox catalysed reactions by our group at CIAE On quantitative structure-activity relationships between hydrazine derivatives and β irradiation,,nuclear Science and Technology, 2017 Quantitative Comparative Kinetics of hydrazine decomposition on platinum under the effect of β radiolysis,manuskript to ACS catalysis Zeolite Y Encapsulated Cu(II) and Zn(II)-Imidazole-Salen Catalysis for Benzyl Alcohol oxidation,journal of Catalysis,accepted Synthesis of amidoxime-grafted activated carbon fibers for efficient removal of uranium(vi) from aqueous solution,chemical Engineering Journal, accpeted

44 Control temperature and TiO2 structure

45 TiO 2 coated NRM particles

Futural optimization of FP particle extraction 1)Extract nano particles from SNF reprocessing residue on the filters, purification by HNO3 HF or H3PO4 in hot HNO3 FP alloy particles can be

46 Futural optimization of FP particle extraction 1)Extract nano particles from SNF reprocessing residue on the filters, purification by HNO3 HF or H3PO4 in hot HNO3 FP alloy particles can be oxidatively dissolved 2) Electrodeposition noble metal elements from HLW 3) High temp., (release/collect I, Cs, enlarge FP alloy particles), crush SNF, high voltage puls fragmentation of SNP to grain size in water and separate FP alloy particles

47 The nonaqueous methods developed for reprocessing spent fuel: fluoride, molybdate, in melts of metals and chlorides, electrochemical,,,,, A. V. Bychkov, O. V. Skiba, Review of Non-Aqueous Nuclear Fuel Reprocessing and Separation Methods, Chemical Separation Technologies and Related Methods of Nuclear Waste Management pp All nonaqueous method expensive and lack of knowledge

48 LOGO

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