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Of Operation and Control Ion-Exchange Processes For TECHNICAL REPORTS SERIES No. 78 Operation and Control Of Ion-Exchange Processes for Treatment of Radioactive Wastes INTERNATIONAL ATOMIC ENERGY AGENCY,VIENNA, 1967 OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES The following States are Members of the International Atomic Energy Agency: AFGHANISTAN GERMANY, FEDERAL NIGERIA ALBANIA REPUBLIC OF NORWAY ALGERIA GHANA PAKISTAN ARGENTINA GREECE PANAMA AUSTRALIA GUATEMALA PARAGUAY AUSTRIA HAITI PERU BELGIUM HOLY SEE PHILIPPINES BOLIVIA HUNGARY POLAND BRAZIL ICELAND PORTUGAL BULGARIA INDIA ROMANIA BURMA INDONESIA SAUDI ARABIA BYELORUSSIAN SOVIET IRAN SENEGAL SOCIALIST REPUBLIC IRAQ SIERRA LEONE CAMBODIA ISRAEL SINGAPORE CAMEROON ITALY SOUTH AFRICA CANADA IVORY COAST SPAIN CEYLON JAMAICA SUDAN CHILE JAPAN SWEDEN CHINA JORDAN SWITZERLAND COLOMBIA KENYA SYRIAN ARAB REPUBLIC CONGO, DEMOCRATIC KOREA, REPUBLIC OF THAILAND REPUBLIC OF KUWAIT TUNISIA COSTA RICA LEBANON TURKEY CUBA LIBERIA UKRAINIAN SOVIET SOCIALIST CYPRUS LIBYA REPUBLIC CZECHOSLOVAK SOCIALIST LUXEMBOURG UNION OF SOVIET SOCIALIST REPUBLIC MADAGASCAR REPUBLICS DENMARK MALI UNITED ARAB REPUBLIC DOMINICAN REPUBLIC MEXICO UNITED KINGDOM OF GREAT ECUADOR MONACO BRITAIN AND NORTHERN IRELAND EL SALVADOR MOROCCO UNITED STATES OF AMERICA ETHIOPIA NETHERLANDS URUGUAY FINLAND NEW ZEALAND VENEZUELA FRANCE NICARAGUA VIET-NAM GABON YUGOSLAVIA The Agency's Statute was approved on 26 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, 1967 Permission to reproduce or translate the information contained in this publication may be obtained by writing to the International Atomic Energy Agency, Kamtner Ring 11, A-1010 Vienna I, Austria. Printed by the IAEA in Austria December 1967 TECHNICAL REPORTS SERIES No. 78 OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA, 1967 OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES (Technical Reports Series, No.78) ABSTRACT. A manual dealing with the application of ion-exchange materials to the treatment of radioactive wastes and reviewing the facilities currently using this method. This book is one of three commissioned by the IAEA on the three principal methods of concentrating radioactive wastes and was prepared by Mr. L.A. Emelity. Contents: Introduction; Historical review related to removal of radioactivity; Principles of ion exchange; Ion-exchange materials; Limitations of ion exchangers; Application of ion exchange to waste processing; Operational procedures and experiences; Costs of treatment by ion exchange; Appendix I - Producers of ex- change materials; Appendix II - Conversions; Appendix III - Regeneration data: specific gravity - concen- tration; Appendix IV - Glossary; Tables; References; Bibliography. Available in English only. (147 pp., 16x24 cm, paper-bound, 31 figures) (1967) Price: USÍ3.00; £1.1.2 OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES IAEA, VIENNA, 1967 STI/DOC/10/78 FOREWORD When facilities are planned for handling radioactive materials, one of the many problems that arise involves the disposal of large-volume low- level wastes. The problem can be tackled by either of two methods: either to 'concentrate and contain' or to 'dilute and disperse'. The choice of method will be guided by the physical, economical, psychological and political environment. The designers of most major installations in the world have chosen to concentrate and contain the wastes, and the three principal techniques of concentration are chemical precipitation, evaporation and ion exchange. Though these techniques are well-established in the chemical processing industry, information on their application to the treatment of radioactive wastes is not readily available. To improve this situation and to give developing Member States some guidance on the solution of this waste-treatment problem, the International Atomic Energy Agency has commissioned books on the three techniques. This particular manual deals with ion exchange and has been compiled by Mr. L.A. Emelity, of Los Alamos Scientific Laboratory, University of California, Los Alamos, New Mexico, USA. Although it is assumed that the basic process is familiar to the reader, history and theory are very briefly mentioned. Ion-exchange materials, their applicationto the treatment of radioactive wastes, and a review of facilities at present using this method are the principal topics. CONTENTS I. INTRODUCTION 1 II. HISTORICAL REVIEW RELATED TO REMOVAL OF RADIOACTIVITY 4 II—1. Reactor systems 4 II—2. Miscellaneous radioactive wastes 5 III. PRINCIPLES OF ION EXCHANGE 8 III—1. General 8 III-2. Characteristics of ion-exchange materials 9 III—2. 1. Ion-exchange capacity 10 III-2.2. Sorption equilibria 10 III—2. 2.1. General 10 III-2.2.2. Donnan membrane equilibrium 11 III-2.3. Swelling equilibrium 12 III-2.4. Ion-exchange equilibrium: selectivity 13 III-2.5. Kinetics 15 III-3. Electrodialysis - Ion-exchange membranes 16 IV. ION-EXCHANGE MATERIALS 19 IV-1. General 19 IV-2. Structure of ion exchangers 19 IV-2.1. General 19 IV-2. 2. Natural inorganic and organic materials 20 IV-2. 3. Synthetic inorganic and organic materials 22 IV-3. Synthesis of ion exchangers 26 IV-3.1. Inorganic ion exchangers 26 IV-3. 2. Organic ion exchangers 27 IV-3.2.1. Condensation polymers 27 IV-3. 2. 2. Addition polymers 29 IV-3.3. Ion-exchange membranes 31 V. LIMITATIONS OF ION EXCHANGERS 32 V-l. Limitations applicable to all ion exchangers 32 V-2. Limitations applicable to natural organic exchangers 33 V-3. Limitations applicable to natural inorganic exchangers 33 V-4. Limitations applicable to synthetic organic exchangers 34 V-5. Limitations applicable to synthetic inorganic exchangers 36 V-5.1. Limitations: synthetic zeolites 36 V-5.2. Limitations: inorganic chemical compounds 36 V-6. Limitations applicable to ion-exchange membranes 37 VI. APPLICATION OF ION EXCHANGE TO WASTE PROCESSING . 38 VI-1. General 38 VI-2. Processing of reactor waters 39 VI-3. Processing of radioactive wastes 40 VI-3.1. General 40 VI-3.2. Treatment methods: batch operation 41 VI-3.3. Treatment methods: column operation 41 VI-4. Design considerations in treatment of reactor waters 46 VI~5. Design considerations in treatment of general laboratory and plant wastes 55 VI~6. Shielding requirements 60 VII. OPERATIONAL PROCEDURES AND EXPERIENCES 64 VII-1. General 64 VII-2. Operational procedures and experiences: treatment of reactor waters 64 VII-3. Experiences in treatment of general plant and laboratory wastes 66 VII-4. Transport of radioactive materials 76 VIII. COSTS OF TREATMENT BY ION EXCHANGE 78 VIII-1. General 78 VIII-2. Capital costs 79 VIII-3. Operating costs 80 APPENDICES I-IV I. PRODUCERS OF EXCHANGE MATERIALS 85 II. CONVERSIONS 86 III. REGENERATION DATA: SPECIFIC GRAVITY - CONCENTRATION 95 IV. GLOSSARY 97 TABLES I-XXVII I. Main components of the radioactivity of reactor coolant water circuits 99 II. Early reactors utilizing ion-exchange demineralization 100 III. Distribution coefficient of caesium on Decalso as a function of sodium concentration 101 IV. Approximate ion-exchange selectivity coefficients 102 V. Relative affinities of ions for a strong-acid resin with varying percentages of crosslinking 103 VI. Comparison of observed selectivity coefficients with values calculated by Myers & Boyd 104 VII. Dependence of ion-exchange rate on experimental control . 105 VIII. Relative ion-exchange rates 106 IX. Variation of resin capacity and moisture content with degree of crosslinking 107 X. Synthetic cation exchangers 108 XI. Natural cation exchangers 116 XII. Synthetic anion exchangers 118 XIII. Mixed bed ion-exchange resins 125 XIV. Ion-exchange membranes 126 XV. Coolant purification in certain early USA power reactors ... 128 XVI. Ion-exchange capacity at varying régénérant levels 129 XVII. Effect of feed rate and temperature on pressure drop 129 XVIII. Resin depth - Ion-exchange column 130 XIX. Principal radionuclides in general waste solutions 131 XX. Exchangers in use for separation of specific radionuclides 132 XXI. Research reactors using ion-exchange water treatment 133 XXII. Ion-exchange treatment of power reactor waters 134 XXIII. Ion exchange in waste treatment at nuclear energy establishments 135 XXIV. Classification of nuclides for transport purposes 136 XXV. Average prices of common engineering materials, October 1966, USA 137 XXVI. Unit operating cost: waste treatment by ion exchange 138 XXVII. Annual operating costs: waste treatment by ion exchange ... 139 REFERENCES 141 BIBLIOGRAPHY 144 I. INTRODUCTION With the rapidly expanding study and use of nuclear energy by an in- creasing number of nations, the problems of control of the radioactive waste products become more acute. Technological advances adapting nuclear physics discoveries to practical applications have followed such discoveries by only brief intervals; quantities and varieties of radioactive wastes have increased at a rate in excess of the development of control technology. Under the pressure of exceedingly limited time, the major effort in attacking the problem has been directed toward adaptation of known techniques in chemical processing and water and wastewater
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