SSC Research Institute of Atomic Reactors. RUSSIA Status of SNF Pyro Reprocessing RIAR, Dimitrovgrad, Russia Mikhail Kormilitsyn Research Institute of Atomic Reactors (RIAR) Radiochemical Complex RIAR General Goal PIE Research Reactors Fuel Supply of BOR-60/MBIR Closing of FC MA recycling Advanced Fuel development and testing RAW Treatment Demo of Closed Fuel Cycle Radionuclide Productions Fundamental Studies R&D for MSR Fuel Cycle 2 New Generation Technological Package “Pyro-Chemistry for CFC” Universal technological platform for decisions in the field of Closed Fuel Cycle of Nuclear Power: • No limitation for: fuel types (oxides, nitrides, metal, carbides, cermet, MSR, IMF) burn up, cooling time • No limitation for requirements of decontamination factor (DF up to 106) 3 New Generation Technological Package “Pyro-Chemistry for CFC” • The Base System – Molten chlorides The Base processes Dissolution of initial SNF ( chlorination or anodic dissolution) Electrolysis on solid and/or liquid cathodes Precipitation Purification of the melt • Option – Technology of fluoride volatility • Option – Partitioning in fluoride melt • Option – chemistry and technology of molten fluoride fuel of MSR 4 R&D on SNF Pyro Reprocessing in a World • Oxide SNF reprocessing into Oxide – RIAR (Russia), JNC/JAEA (Japan) • Oxide SNF reprocessing into Metallic – CRIEPI (Japan), KAERI (Korea) • Nitride SNF reprocessing – JAERI/JAEA (Japan), RIAR (Russia) • Metallic SNF reprocessing – INL, ANL (US), CRIEPI (Japan), RIAR (Russia) • SNF metallization – KAERI (Korea), RIAR (Russia) • HLW partitioning in molten salts – CRIEPI (Japan), RIAR (Russia), KAERI (Korea), CEA (France), ITU (EU) • Fluoride volatility processes – CRIEPI, Hitachi/TEPCO (Japan), Kurchatov Inst., RIAR (Russia), INR (Czech. Rep.) • MSR Fuel Cycle – RIAR, Kurchatov Inst., CNRS (France), Institute for Applied Physics, Shanghai (China) • Other application 5 RIAR Experience 6 RIAR activities in the field of CFC Since 1964 RIAR has been pursuing large-scale investigations in the following research lines: Pyrochemical production technology of vi-pack U and MOX fuel Pyrochemical reprocessing of SNF from nuclear reactors of various types . Fluoride volatility reprocessing of SNF 7 Milestones of Experience in Closed Fuel Cycle • Pyro R&D- from early 1960-s • Demo of fluoride volatility reprocessing – 1970s • Pilot facility for pyro/vi-pack MOX fuel production for fast reactor – from late 1970-s • BOR-60 full scale fuel supplying only on the base of own RIAR pyro/vi-pack fuel production facilities – from 1980 • Pyro reprocessing experience – from 1991 • Study on transmutation cycle, nitride fuels and others – from 1992 • Start of industrial implementation of pyro/vi-pack MOX technology – 2012 • Start of so called “high density” FR SNF (nitride, metal) - 2010 • Creation of “Poly-functional Radiochemical Complex” (PRC) 2010-2017 8 RIAR experience in reprocessing of spent fuel of the BOR-60 and BN-350 reactors Fuel type Burn-up % h.a. Cooling time, Yrs UO2 7,7 5 2,5 1972..1973 BN-350 MOX 4,7 10 4,1 1991 BN-350 MOX 21..24 1-2 6,5 1995 BOR-60 UO2 10 15 5 2000 BOR-60 MOX 10 10 12 2000…2001 BOR-60 MOX 16 4-6 5 2004 BOR-60 U-Pu /Na 6,4 19 0,13 2010 BOR-60 (U,Pu)N /Pb 0,53 8 0,28 2010 BOR-60 U-Zr / Na 9,7 9,5 0,12 2010 BOR-60 U-Pu-Zr /Na 9,7 9,5 0,10 2010 BOR-60 MOX 15 5 4 2011 BOR-60 Weight, kg Date Reactor 9 Dimitrovgrad Dry Process (DDP) – MOX Fuel Pyro processing Basic research of the molten salt systems allowed for the development of technological processes for production of granulated U and Pu dioxides and MOX. A distinctive feature of the Pyro technology is a possibility to perform all the deposit production operations in one apparatus - a chlorinator-electrolyzer Pyrochemical reprocessing consists of the following main stages • Dissolution of initial products or spent nuclear fuel in molten salts • Recovery of crystaline Pu dioxide electrolytic MOX from the melt • Processing of the cathode deposit and production of vi-pack or 10 Production and testing of vi-pack MOX fuel Fuel type Number of FAs Burn-up, max.% Load, kW/m Temperature, 0С Reactor (U, Pu)O2 Civil grade/ or weapon quality 330 30,3 51,5 720 BOR-60 UO2 + PuO2 Civil grade/ or weapon quality 132 14,8 45 705 BOR-60 (U, Pu)O2 Weapon grade 26 11,1 46 680 BN-600 (U, Pu)O2 Civil grade 4 development of the production technique BN-600 11 Cl2 Stirrer Na3PO4 Cathode (pyrographite) Ar (Cl2) Cl2+O2+Ar Cathode Cl2+O2+Ar Stirrer Stirrer pyrographite bath, NaCl - KCl + UO22+ O2 UO2 + NpO2 Pu4+ UO2 + UO22+ MA,RE E UO2 Pu4+ UO22+ NpO2+ PuO2 Fuel chlorination 700 оС PuO22+ PuO2 Preliminary electrolysis 680 оС (MA,REE) RW4 UO22+ Precipitation crystallization 680 оС Cl- Electrolysisadditional 700 оС Melt purification 700 оС DDP MOXPuO2 flow sheet Stirrer Cl2 Cathode (pyrographite) Cl2+O2+Ar Ar (Cl2) Na3PO4 Cathode Cl2+O2+Ar Stirrer pyrographite bath, NaCl -2CsCl + + UO22+ UO2 Pu4+ PuO2 Fuel chlorination 650 оС UO2 + NpO2 UO22+ NpO2+ Preliminary electrolysis 630 оС MOX UO22+ PuO2+ Main MOX electrolysis 630 оС + MOX UO22+ PuO2+ Electrolysisadditional 630 оС DDP MOXMOX flow sheet MA,RE E Cl- (MA,REE) RW4 Melt purification 6500 оС 12 MOX-MOX Reprocessing 2004 Year MOX - 3 400 g Pu content - 33,5 % wt. 2000 Year MOX - 3 200 g Pu content - 10 % wt. 13 Pyro HLW treatment Na3PO4 Pyroreprocessing Salt purification Radioactive Cs Fission products Phosphates Waste NdPO4C ePO4 Salt residue NaCl CsCl Phosphates Salt residue Special features contain fission products Alkaline metal chlorides, high activity, significant heat release Basic elements 11 wt.% Nd 4,4 wt.% Ce 81,96 wt.% CsCl 18,04 wt.% NaCl Quantity* <0,15 kg/kg of fast reactor SNF * - TOSHIBA estimation for DDP <0,03 kg/kg of fast reactor SNF 14 Vitrification of HLW from pyro process HLW type Characteristic Glass matrix type Introduction method Introduced waste amount, % 137Cs leaching rate as of the 7th day, g/cm2 * day Thermal resistance, 0С Radiation resistance Phosphate precipitate Spent salt electrolyte Phosphate precipitate + spent salt electrolyte Pb(PO3)2 NaPO3 NaPO3, AlF3 Al2O3 NaPO3, AlF3 Al2O3 vitrification, Т=9500С vitrification without chloride conversion, Т=9500С vitrification without chloride conversion, Т=9500С 28 20 36 7*10-6 7*10-6 4*10-6 400 400 400 107 Gr (for and ) 1018 -decay/g 15 Ceramization of HLW arising from pyro process Type of high-level wastes Characteristics Phosphate deposit Spent salt electrolyte monazite Cosnarite (NZP) pressing, calcination , Т=8500С Conversion to NZP from the melt or aqueous solution, pressing, calcination , Т=10000С Quantity of waste introduced into ceramics, % 100 30..40 Leaching rate of 137Cs on 7-th day, g/cm2 * day 1*10-6 3*10-6 850 1000 Type of ceramics Method of introduction into ceramics Thermal stability, 0С Radiation resistance 5*108 Gy( for and ) 1019 - decay/g 16 RIAR R&D PROGRAM DOVITA Since 1992 • Dry technologies • Oxide fuel with MA • Vi-pack • Integrated disposition on the same site with the reactor • TA Transmutation of Actinides 17 18 Experience in DOVITA Program Pyrochemical technology of adding Np into oxide fuel (520%) has been developed Performance of vi-pack fuel with (U,Np)O2 fuel has been validated experimentally to ~20% burnup in BOR-60 No evidence of significant difference in performance of fuel rods with (U,Np)O2 fuel compared with UO2 or MOX fuel rods has been noticed Pyrochemical process of codeposition of Am with MOX fuel (2-4%) has been developed Methods of Am/REE separation in melts has been tested Irradiated (U,Np)O2 fuel, 19% burn-up Special vi-pack targets containing Am oxide with UO2 or inert matrix have been developed Transmutation of Np, Am, Cm is being studied in BOR-60 19 New times consideration: DOVITA 1992 Dry technologies Oxide fuel with MA Vi-pack Integrated disposition same site with the reactor TA Transmutation of Actinides DOVITA-2 2007+ Dry technologies On-site reprocessing Various type of fuel with MA Integration of MA recycling into FR Closed Fuel Cycle TA - Transmutation of Actinides 20 DOVITA-2 Fuel type/ Oxide Stages vi-pack Concept Studies + Oxide pellet + Nitride vi-pack + Metal +/- Molten salt + R&D + -/+ +/- - + Fuel Production + - - - - Irradiation Testing PIE + - - - - + - - - ---- Reprocessing -/+ - - - +/- DOVITA-1 21 Current R&D 22 In the Frame of Federal Target Program For the First Time in a World – pyrochemical reprocessing of FBR spent U-Pu nitride fuel and metal fuel ~ 0,6 kg SF 2 Cd ingots for fabrication of fuel Oxide concentrate FP for wastes preparation 23 Experimental Tests of Spent Nitride Fuel Reprocessing Methods The empty pies of cladding after anodic dissolution of nitride SNF in chloride melt The sample of fluoride-phosphate glass with real immobilized FPs after reprocessing 24 100% PuO2 Pyro Pellets PuO2 Pellets Characteristics Melted salt 3LiCl-2KCl NaCl-2CsCl Pellets density, g/sm3 8.5-10.2 9.8-10.3 Visual view no cracks no cracs PuO2 Pellets (3LiCl-2KCl, T=450oC) PuO2 Pellets (NaCl-2CsCl, T=550oC) 25 80%UO2 + 20%PuO2 MOX Pyro Pellets MOX Pellets Characteristics Batch № 1 Technical Requirements* Pellet density, g/sm2 10.2-10.4 10.2-10.7 Deviation of pellet density, g/sm2 +0.1 +0.1 O/Me 1.98 1.97+0.01 Impurities content, % масс. <0.3 <0.4 Average size of crystalline granules, microns 30-40 < 50 Visual view no cracks no cracks Porosity uniform uniform *Reshetnikov Ph.G. and et al. Working out, production and operation of fuel rods of power reactors-M:.Energoizdat, 1995-320p. 26 Pyro MOX pellets (80%UO2 + 20%PuO2) Microstructure of MOX pellets Content, wt% Массовая доля U, Pu,% EPMA 90 80 70 60 50 40 30 20 10 0 3000 3500 4000 U 4500 Pu 5000 5500 6000 Расстояние, мкм μm Unpickled pellet Pickled pellet Solubility test in 8M HNO3 at 95-96оC , duration – 10 hrs. Composition of pellet 80wt%UO2 +20wt%PuO2 Medium of powder production Insoluble residue, % wt. Residue composition, wt% 3LiCl-2KCl 0.14 (Pu0.81, U0.19)O2 3LiCl-2KCl 0.14 (Pu0.49, U0.51)O2 NaCl-2CsCl 0.40 (U0.65, Pu0.31,Am0.04)O2 27 Fuel pin #TM0-01 with pyro MOX pellets Dismountable BOR-60 FAs 28 Fundamental Studies Curium containing salt for spectroscopy studies NaCl-2CsCl-CmCl3(0.115mol/kg) 29 transmission density Spectrum of curium-containing melt under atmosphere of Ar- HCl-H2O CmO+ 0.55 Cm3+ 0.25 Am3+ -0.05 320 370 420 470 520 wave-length, nm NaCl-2CsCl-CmCl3(0.115mol/kg) 750oC log(P2HCl/PH2O)=-7.14 30 Synchronized potentiometric titration by oxygen pump and spectroscopy Oxygen pump CE RE Gas-supply tube Oxygen sensor Cavity from optical quartz 31 MA and FP Partitioning T,oC Run # Weight, g Content in melt, % (Li,K,Cs)Cl Ga Am Ce E, V 1 350 200 95 0.6 3 -1.2 2 350 200 95 0.6 3 -1.4 3 350 200 95 0.6 3 -1.6 Ga cathod 0 -0.2 -0.4 I, A -0.6 -0.8 -1 -1.2 -1.4 -1.6 0 200 400 600 800 1000 1200 1400 Time, sec 32 Experimental Facilities till 2020 34 CFC Pyro technology for International RIAR-based Center of Excellence RIAR Site Post Irradiation Examination electricity Heat power radionuclides R&D on Reprocessing MBIR MOX or other fuel and Refabrication of Advanced Fuels Post Irradiation complex RadioWaste complex Вибро Vi-pack Отходы на хранение RAW Radiochemical Complex Refabricated Fuel RIAR Radiochemical Complex Пиро Pyro MOX ChemicalProduction Technological Facility complex 35 Federal Tasks-oriented Program “New Generation Nuclear Power Technologies” • Large Poly-functional Radiochemical Complex (PRC) - 2017 Molten salt Reprocessing Facility (1st hot cell line) capacity – up to 1-2 tons of FR SNF per Year (fuel type: oxide, nitride, metallic, IMF) Advanced water-technology Facility, (2nd hot cell line) capacity – up to 1-2 tons kg of SNF per Year • New Lab for Experimental and Innovative Fuel Production – 2010-1017 (incl. Fuel and Targets with MA) • New facility for HLW treatment • Demonstration of Closing Fuel Cycle • Testing and Demonstration of Closing FR Fuel Cycle for MA • Develop the full scale Design of Industrial plants for FR SNF Reprocessing 36 List of Advanced R&D for PRC • • • • • • Testing of prototypes of technological equipment Development and testing of automatic and robotics systems Comparative FS for different technologies Advanced thermo-chemical decladding technologies Voloxidation Pyrochemical molten salt technologies • MOX fuel Mixed Nitrides Metallic IMF, MSR Remote control fabrication technologies Vi-pack Pelletizing Metallic • RAW treatment • • Vitrification Ceramization 37 37 38 THANK YOU FOR ATTENTION! RIAR Radiochemical Complex 38