Use of Local Minerals in the Treatment of Radioactive Waste
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O = 0(0H) •=Si(AI) O = 0(0H) # = AI, Mg, Fe, etc. TECHNICAL REPORTS SERIES No. 136 Use of Local Minerals in the Treatment of Radioactive Waste INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 1972 USE OF LOCAL MINERALS IN THE TREATMENT OF RADIOACTIVE WASTE The following States are Members of the International Atomic Energy Agency: AFGHANISTAN GUATEMALA PAKISTAN ALBANIA HAITI PANAMA ALGERIA HOLY SEE PARAGUAY ARGENTINA HUNGARY PERU AUSTRALIA ICELAND PHILIPPINES AUSTRIA INDIA POLAND BELGIUM INDONESIA PORTUGAL BOLIVIA IRAN ROMANIA BRAZIL IRAQ SAUDI ARABIA BULGARIA IRELAND SENEGAL BURMA ISRAEL SIERRA LEONE BYELORUSSIAN SOVIET ITALY SINGAPORE SOCIALIST REPUBLIC IVORY COAST SOUTH AFRICA CAMEROON JAMAICA SPAIN CANADA JAPAN SUDAN CEYLON JORDAN SWEDEN CHILE KENYA SWITZERLAND CHINA KHMER REPUBLIC SYRIAN ARAB REPUBLIC COLOMBIA KOREA, REPUBLIC OF THAILAND COSTA RICA KUWAIT TUNISIA CUBA LEBANON TURKEY CYPRUS LIBERIA UGANDA CZECHOSLOVAK SOCIALIST LIBYAN ARAB REPUBLIC UKRAINIAN SOVIET SOCIALIST REPUBLIC LIECHTENSTEIN REPUBLIC DENMARK LUXEMBOURG UNION OF SOVIET SOCIALIST DOMINICAN REPUBLIC MADAGASCAR REPUBLICS ECUADOR MALAYSIA UNITED KINGDOM OF GREAT EGYPT, ARAB REPUBLIC OF MALI BRITAIN AND NORTHERN EL SALVADOR MEXICO IRELAND ETHIOPIA MONACO UNITED STATES OF AMERICA FINLAND MOROCCO URUGUAY FRANCE NETHERLANDS VENEZUELA GABON NEW ZEALAND VIET-NAM GERMANY, FEDERAL REPUBLIC OF NIGER YUGOSLAVIA GHANA NIGERIA ZAIRE, REPUBLIC OF GREECE NORWAY ZAMBIA The Agency's Statute was approved on 23 October 1956 by the Conference on the Statute of the IAEA held at United Nations Headquarters, New York; it entered into force on 29 July 1957, The Headquarters of the Agency are situated in Vienna. Its principal objective is "to accelerate and enlarge the contribution of atomic energy to peace, health and prosperity throughout the world". © IAEA, 1972 Permission to reproduce or translate the information contained in this publication may be obtained by writing to the International Atomic Energy Agency. Kärntner Ring 11, P.O. Box 590, A-1011 Vienna, Austria. Printed by the IAEA in Austria June 1972 TECHNICAL REPORTS SERIES No. 136 USE OF LOCAL MINERALS IN THE TREATMENT OF RADIOACTIVE WASTE INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA, 1972 USE OF LOCAL MINERALS IN THE TREATMENT OF RADIOACTIVE WASTE IAEA, VIENNA, 1972 STl/DOC/10/136 FOREWORD A great deal of information has been made available on the various techniques in use for safely managing radioactive waste. The International Atomic Energy Agency periodically convenes panels or other meetings to bring this information up to date and publishes Safety Series, Technical Reports Series and Guidebooks to help disseminate this information. Technical Reports Series No. 78, 'Operation and Control of Ion- Exchange Processes for Treatment of Radioactive Wastes' , published by the Agency in 1967, deals with the use of high capacity organic and in- organic exchange materials. A need has been expressed by developing countries for more information on the use of locally available ion-exchange and sorbent materials. The present publication, which is the outcome of a panel meeting, on the Use of Local Minerals in the Treatment of Radioactive Waste, held at the Agency's Headquarters in Vienna on 5-9 May 1969, presents, for the first time in a single volume, the large amount of practical information available. A list of the panel participants and the advisers appears at the end of the book. These experts kindly provided the material for the publication, which was organized by Mr. E.W. Wiederhold of the IAEA. CONTENTS I. INTRODUCTION 1 II. NATURAL MATERIALS FOR RADIOACTIVE WASTE TREATMENT 3 II. 1. Introduction 3 11.2. Types of reaction mechanism 3 11.2.1. Distribution of the radioactive microcomponent between solid and liquid phases 3 11.2.2. Co-precipitation 3 11.2.3. Coagulation and flocculation of colloids 6 11.2.4. Adsorption from solutions 9 11.2.5. Ion exchange 10 11.2.5.1. Ionic crystals 10 11.2.5.2. Aluminosilicates 12 11.2.6. Mineral replacement reactions 17 11.2.7. Oxidation-reduction mechanisms 19 11.2.7.1. Redox exchangers 19 11.2.7.2. Examples 19 11.2.7.3. Applications 20 11.3. Materials 20 11.3.1. Introduction 20 11.3.2. Mineral classification scheme 21 11.3.3. Minerals of use in waste treatment 21 11.3.4. Oxides and hydroxides 23 11.3.5. Halides 23 11.3.6. Carbonates 24 11.3.7. Phosphates 25 11.3.8. Sulphates 26 11.3.9. Silicates 26 11.3.9.1. Layer silicates 26 11.3.9.2. Zeolites 27 11.3.9.3. Crystal chemistry of the clays and zeolites 27 11.3.9.4. Waste treatment applications — 29 11.3.10. Other naturally occurring substances 30 III. CHARACTERIZATION OF MATERIALS 31 III.l. Sampling 31 III. 1.1. Sampling in the field 31 III.1.2. Laboratory sample preparation 32 III.1.2.1. Microscopic examination 32 111.1.2.2. Crushing 32 111.1.2.3. Sieving 32 111.1.2.4. Separation methods 33 111.2. Identification of the material 33 111.2.1. X-ray diffraction 33 111.2.2. Electron microscopy and electron diffraction 34 111.2.3. Petrographic microscopy 34 111.2.4. Thermal methods 35 111.2.5. Infrared spectrometry 35 111.2.6. Chemical methods of material identification 36 111.3. Physico-chemical characterization 36 111.3.1. General remarks 36 111.3.2. Capacities 36 111.3.2.1. Definitions 36 111.3.2.2. Pure ion exchange capacity (Kr) 37 111.3.2.3. Sorption capacity (K ad) 37 111.3.2.4. Total exchange capacity (Ktot) 38 111.3.2.5. Procedures 38 111.3.2.6. Complications 39 111.3.3. Selectivity 39 111.3.3.1. Ion exchange equilibrium 40 111.3.3.2. Ion exchange isotherm 40 111.3.3.3. Distribution coefficient (K*) 41 41 111.3.3.4. Separation factor (OB ) 111.3.3.5. Selectivity coefficient (NKB) 42 111.3.3.6. Procedures 42 111.3.4. Kinetic properties 42 111.3.4.1. Definitions 43 111.3.4.2. Procedures 43 111.3.5. Swelling properties 44 111.3.5.1. Definitions 44 111.3.5.2. Procedures 45 111.3.6. Reduction-oxidation properties 45 111.3.6.1. Redox capacity 45 Definition 45 Procedure 45 111.3.6.2. Redox potential 46 IV. MATERIALS 47 IV.1. Material preparation 47 IV.1.1. Crushing and grinding 47 IV.1.2. Sieving (screening) 48 IV.1.3. Washing 51 IV.2. Chemical and heat pre-treatment 52 IV.2.1. Chemical pre-treatment 52 IV.2.2. Heat pre-treatment 54 IV.2.3. Pelletizing 56 IV.2.3.1. Heat treatment of bentonites 56 IV.2.3.2. Heat treatment of alumina and clinoptilolite 56 V. PLANT SCALE APPLICATIONS 57 V.l. General 57 V.l.l. Ion exchangers 57 V.l.1.1. Batch process 57 V.l.1.2. Column operation 57 V.l.2. Additives and product conditioners 59 V.2. Operational experience 59 V.2.1. United Kingdom (Harwell) 59 V.2.2. India (Trombay) 61 V.2.3. United States of America 61 V.2.3.1. National Reactor Testing Station (NRTS), Idaho 61 V.2.3.2. O&k Ridge National Laboratory 64 V.2.3.3. Battelle North West Laboratory, Richmond 65 V.2.3.4. Savannah River 65 V.2.4. Federal Republic of Germany 65 V.2.5. Czechoslovak Socialist Republic 66 VI. FINAL PRODUCT CONDITIONING 67 VI.1. Conditioning of exhausted inorganic ion exchangers 67 VI.1.1. Treatment at Idaho Falls 67 VI.1.2. Treatment at Harwell 67 VI. 1.3. Incorporation into bitumen or concrete 67 VI.1.4. Fixation in glasses 68 VI.1.5. Reduction of leachability by heat treatment 68 VI.2. Use of inorganic minerals for improvement of fixed radioactive wastes 68 VII. ECONOMIC ASPECTS 71 VII.1. Capital costs 71 VII.2. Operating costs 72 APPENDIX I: NATURAL MATERIALS FOR USE IN WASTE TREATMENT 73 APPENDIX II: DEFINITION AND DETERMINATION OF CAPACITIES OF NATURAL ION EXCHANGERS .... 81 1. Introduction 81 2. Elementary principles 82 3. Definitions of ion exchange capacity 83 4. General methods of determination 92 References to Appendix II 95 APPENDIX III: COMMUNICATIONS CONCERNING NATIONAL EXPERIENCE IN VARIOUS COUNTRIES 97 1. France 97 2. Germany, Federal Republic of 97 3. Italy 98 4. Korea 99 5. Union of Soviet Socialist Republics 99 Special communication by V.M. Sedov, USSR: Research in the USSR on the use of natural sorbents for radioactive waste treatment 99 REFERENCES 107 LIST OF PARTICIPANTS 113 I. INTRODUCTION In 1962 the Agency convened an ad hoc panel on Radioactive Waste Disposal into the Ground. This panel was primarily concerned with the rate of movement of ground water and radioactive isotopes through soil. Ion exchange with and sorption by naturally occurring zeolites and clays were discussed. Replacement reactions, in which a slightly soluble mineral in the soil is gradually replaced by a less soluble species by reacting with an appropriate ion in the solution, were also discussed. In 1964 the Agency convened another panel relating to the use of minerals in the treatment of radioactive wastes. This panel was on the Application of Mineral Reactions in Radioactive Waste Treatment. Much useful information was presented and a variety of mineral reactions were discussed. Among the topics discussed were mineral species used as aids in flocculation, as sorbents or exchange media in beds or columns, as sorbents or exchange media which remove the activity from discharges to the ground and those species which tend to concentrate activity in the sediments of streams, lakes and oceans. Much work had been done on the various clays, vermiculite, zincite, pyrolusite and zeolites.