science XN9800106 OCDE Actinide Separation Nuclear Waste Streams and Materials 29-3 NEA NUCLEAR ENERGY AGENCY O M NEA/NSC/DOC(97)19 NEA NUCLEAR SCIENCE COMMITTEE ACTEVIDE SEPARATION CHEMISTRY IN NUCLEAR WASTE STREAMS AND MATERIALS December 1997 NUCLEAR ENERGY AGENCY ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT ORGANISATION AN Pursuant to Article 1 of the Convention signed in Paris on 14th December 1960, and which came into force on 30th September 1961, the Organisation for Economic Co-operation and Development (OECD) shall promote policies designed: — to achieve the highest sustainable economic growth and employment and a rising standard of living in Member countries, while maintaining financial stability, and thus to contribute to the development of the world economy; — to contribute to sound economic expansion in Member as well as non-member countries in the process of economic development; and — to contribute to the expansion of world trade on a multilateral, non-discriminatory basis in accordance with international obligations. The original Member countries of the OECD are Austria, Belgium, Canada, Denmark, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, the Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, Turkey, the United Kingdom and the United States. The following countries became Members subsequently through accession at the dates indicated hereafter: Japan (28th April 1964), Finland (28th January 1969), Australia (7th June 1971), New Zealand (29th May 1973), Mexico (18th May 1994) the Czech Republic (21st December 1995), Hungary (7th May 1996), Poland (22nd November 1996) and the Republic of Korea (12th December 1996). The Commission of the European Communities takes part in the work of the OECD (Article 13 of the OECD Convention). NUCLEAR ENERGY AGENCY The OECD Nuclear Energy Agency (NEA) was established on 1st February 1958 under the name of the OEEC European Nuclear Energy Agency. It received its present designation on 20th April 1972, when Japan became its first non-European full Member. NEA membership today consists of all OECD Member countries, except New Zealand and Poland. The Commission of the European Communities takes part in the work of the Agency. The primary objective of the NEA is to promote co-operation among the governments of its participating countries in furthering the development of nuclear power as a safe, environmentally acceptable and economic energy source. This is achieved by: — encouraging harmonization of national regulatory policies and practices, with particular reference to the safety of nuclear installations, protection of man against ionising radiation and preservation of the environment, radioactive waste management, and nuclear third party liability and insurance; — assessing the contribution of nuclear power to the overall energy supply by keeping under review the technical and economic aspects of nuclear power growth and forecasting demand and supply for the different phases of the nuclear fuel cycle; — developing exchanges of scientific and technical information particularly through participation in common services; — setting up international research and development programmes and joint undertakings. In these and related tasks, the NEA works in close collaboration with the International Atomic Energy Agency in Vienna, with which it has concluded a Co-operation Agreement, as well as with other international organisations in the nuclear field. ©OECD 1997 Permission to reproduce a portion of this work for non-commercial purposes or classroom use should be obtained through Centre francais a'exploitation du droit de copie (CCF), 20, rue des Grands-Augustins, 75006 Paris, France, for every country except the United States. In the United States permission should be obtained through the Copyright Clearance Center, Inc. (CCC). All other applications for permission to reproduce or translate all or part of this book should be made to OECD Publications, 2, rue Andr6-Pascal, 75775 PARIS CEDEX 16, France. FOREWORD The separation of actinide elements from various waste materials is a significant: problem fimg developed countries. The issue arises primarily because of the potential long-term hazard of many of the Sdes bmis also due to the regulatory requirements associated with actinide waste disposal, which SdtfSent from those associated with other radioactive wastes. The different regulations are m turn related to *edifferent health hazards and generally longer half lives of the actmides. This issue is of interest to the OECD/NEA Member countries primarily in relation to waste produced wrfhm uel recycle. Similar problems exist for waste produced in the past as a result of nuclear ^T^on programmes L wastes likely to be produced in the future emerging from operations required for waste disposal. listed in Annex 1. This report is intended to provide a timely and representative guide to technical journals and other soured o^separation chemistry information on the actinide elements. An important objective 1S to Provide information that may be used to conserve energy and protect humans and the environment. The areas discussed include sources, types and amounts of actinide wastes and their relative ioL using a 25 year horizon for those needs as a practical extension into the future. For related material see http://www.nea.fr/html/science/chemistry/ the responsibility of the Secretary-General of the OECD. on Acknowledgement The authors wish to acknowledge Professors Jan-Olov Liljenzin of Goteborg, Sweden Gregor^ ChoppTn o^Tallahassee, Florida, and Robert Guillaumont of IPN, France for their critical reviews and excellent suggestions for improvements to this report. NEXT PAQE(S) left BLANK TABLE OF CONTENTS EXECUTIVE SUMMARY 13 Section 1. INTRODUCTION 15 1.1 Relationship of the Task Force on Actinide Separation Chemistry to the NEA and the NSC 15 1.2 Importance of the report to waste management 15 1.3 Importance of the report to Member countries 16 1.4 International waste stream treatment activities 16 1.5 Nature of waste streams 16 1.6 Management schemes 18 1.7 Reduction in amounts of wastes discharged into the environment 18 1.8 Scope and objectives 18 Section 2. TYPES OF WASTE STREAMS 19 2.1 Reasons for importance 19 2.1.1 Hazards, limits 20 2.1.2 Quantities 20 2.1.2.1 Fuel 20 2.1.2.2 Tank wastes 21 2.1.2.2.1 Hanford 21 2.2 By physical form 23 2.2.1 Solids 24 2.2.2 Aqueous solutions 24 2.2.2.1 High ionic strength 24 2.2.2.2 Low ionic strength 26 2.2.3 Sludges 27 2.2.4 Colloids 27 5 2.3 By sources of actinides 27 2.3.1 Residues from mining, milling and purification 27 2.3.2 Residues from conversion and enrichment 28 2.3.3 Back-end of the fuel cycle 28 2.3.3.1 Discharged nuclear fuel for direct disposal 28 2.3.3.2 High-level waste 28 2.3.3.3 Intermediate-level waste 28 2.3.3.4 Low-level wastes (solid and liquid) 29 2.3.3.5 US military wastes in priority order 29 2.3.3.6 Sludges from effluent treatment 30 2.3.3.7 Discarded solvent 30 2.3.3.8 Decontamination liquors 30 2.3.4 Clean-up operations 31 2.3.5 Isotopic source preparation 31 2.3.6 Natural and non-nuclear industrial sources 31 2.4 Orphan fuels 31 2.4.1 US DOE fuels 32 Section 3. BASIC CHEMICAL DATA 33 3.1 Actinide chemical thermodynamics 34 3.1.1 Solutions 34 3.1.1.1 Ionic radii 34 3.1.1.2 Oxidation states 34 3.1.1.3 Hydrolysis and complexation 36 3.1.1.3.1 Hydrolysis and complex formation with simple inorganic ligands 36 3.1.1.3.2 Complexes with simple organic ligands 37 3.1.1.3.3 Complexes with polyorganic acids 38 3.1.1.4 Hydrolytic polymers, solubility and colloid formation 38 3.1.1.5 Sorption/desorption 39 3.1.1.6 Non-aqueous media 40 3.1.1.6.1 Gibbs energies of formation of halides 40 6 3.1.2 Solids 41 3.1.2.1 Gibbs energies of formation 41 3.1.2.2 Solid waste phases 41 3.1.2.3 Actinides in refractory matrices 41 3.1.3 Volatile compounds 41 3.1.3.1 Volatility of metals 42 3.1.3.1.1 Pure metals 42 3.1.3.1.2 Solutions of metals 42 3.1.3.2 Volatility of fluorides 42 3.1.3.3 Volatility of chlorides 43 3.2 Radiolysis 43 3.3 Actinide analysis related to separation processes 45 3.3.1 Analysis in liquids and solids 45 3.3.1.1 Packaged (or "workshop") wastes 45 3.3.1.2 At the laboratory 45 3.3.1.3 Other 46 Section 4. STATE OF THE ART IN ACTINIDE SEPARATION CHEMISTRY 47 4.1 Hydrometallurgy 47 4.1.1 Liquid-liquid extraction 47 4.1.1.1 PUREX 48 4.1.1.2 IMPUREX 48 4.1.1.3 TRUEX 48 4.1.1.4 D1AMEX 49 4.1.1.5 TRPO 49 4.1.1.6 DIDPA extraction 49 4.1.1.7 TALSPEAK 50 4.1.1.8 TRAMEX 50 4.1.1.9 Advanced separations 50 4.1.1.9.1 Crown ethers 51 4.1.1.9.2 Beta-diketones 51 4.1.1.9.3 Picolinamides 51 4.1.1.9.4 Diphosphonic acids 51 4.1.1.9.5 Calixarenes 52 4.1.1.9.6 TPTZ 52 4.1.1.9.7 SESAME process 52 4.1.2 Precipitation 52 4.1.2.1 Actinide compounds 53 4.1.2.1.1 Oxalate 53 4.1.2.1.2 Carbonate 53 4.1.2.1.3 Peroxide 53 4.1.2.1.4 Fluorides 53 4.1.2.1.5 Uranates 54 4.1.2.1.6 Hydroxides 54 4.1.2.1.7 Colloids/pseudocolloids 54 4.1.2.2 Co-precipitation 54 4.1.2.2.1 Scavenging 55 4.1.2.2.2 Bismuth phosphate 55 4.1.3 Chromatography 55 4.1.3.1 Organic ion exchange 55 4.1.3.1.1 Macroporous resins 57 4.1.3.1.2 Radiation resistant resins 57 4.1.3.1.3 Multifunctional chelating resins 58 4.1.3.2 Extraction chromatography 58 4.1.3.2.1 CMP and CMPO 58 4.1.3.2.2 Hollow fibre 58 4.1.3.3 Continuous annular chromatography 59 4.1.3.4 Biosorption 59 4.1.3.5 Inorganic ion exchange 60 4.1.3.5.1 "Inclusion" exchangers 60 4.1.3.5.2 Matrix supported 61 4.1.4 Membrane techniques 61 4.1.4.1 Supported liquid membranes 61 4.1.4.2 Ion exchange membranes