Else_SIBE-ANDREEV_prelims.qxd 10/10/2006 5:27 PM Page i Separation of Isotopes of Biogenic Elements in Two-phase Systems This page intentionally left blank Else_SIBE-ANDREEV_prelims.qxd 10/10/2006 5:27 PM Page iii Separation of Isotopes of Biogenic Elements in Two-phase Systems B.M Andreev, E.P Magomedbekov, A.A Raitman, M.B Pozenkevich, Yu.A Sakharovsky, A.V Khoroshilov D Mendeleev University of Chemical Technology Moscow, Russian Federation Amsterdam ● Boston ● Heidelberg ● London ● New York ● Oxford Paris ● San Diego ● San Francisco ● Singapore ● Sydney ● Tokyo Else_SIBE-ANDREEV_prelims.qxd 10/10/2006 5:27 PM Page iv Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK First edition 2007 Copyright © 2007 Elsevier B.V All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (ϩ44) (0) 1865 843830; fax (ϩ44) (0) 1865 853333; email: permissions@elsevier.com Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN-13: 978-0-444-52981-7 ISBN-10: 0-444-52981-0 For information on all Elsevier publications visit our website at books.elsevier.com Printed and bound in The Netherlands 07 08 09 10 11 10 Else_SIBE-ANDREEV_contents.qxd 10/13/2006 2:01 PM Page v Contents Preface Introducton Theory of Isotope Separation in Counter-Current Columns: General Review 1.1 Separation Factor 1.2 Kinetics of CHEX Reactions and Mass Exchange in Counter-Current Phase Movement 1.3 Stationary State of the Column with Flow Reflux 1.4 Unsteady State of the Column and Cascades of Columns 1.5 Separation Column Contactors 1.5.1 Types and characteristics of packing 1.5.2 Hydrodynamics of countercurrent gas (vapour)–liquid two-phase flows in the packing material layer References Hydrogen Isotope Separation by Rectification 2.1 D2O Production by Water Rectification 2.2 Heavy Water Production by Ammonia Rectification 2.3 Heavy Water Production by Cryogenic Rectification of Hydrogen 2.3.1 Fundamentals 2.3.2 Hydrogen rectification for deuterium extraction 2.4 Isotope Extraction and Concentration of Tritium 2.4.1 The use of deuterium cryogenic rectification for heavy water purification for nuclear reactor circuit 2.4.2 Separation of isotopes in the system of deuterium–tritium fuel cycle of thermonuclear power reactor References ix xi 1 12 23 29 29 30 39 41 41 45 50 50 52 55 55 62 70 Hydrogen Isotope Separation by Chemical Isotope Exchange Method in Gas-Liquid Systems 73 3.1 Two-Temperature Method and Its Main Features 73 3.1.1 Basic two-temperature schemes and cascades of two-temperature plants 73 3.1.2 Extraction degree 78 3.1.3 Steady state of the two-temperature plant 80 3.1.4 Effect of mutual solubility of phases 86 3.1.5 Unsteady state of two-temperature plant 91 3.2 Two-Temperature Hydrogen Sulphide Method 93 3.2.1 Phase equilibrium and isotope equilibrium 93 3.2.2 Kinetics of isotope exchange: packing materials 99 3.2.3 Heat recovery 111 v Else_SIBE-ANDREEV_contents.qxd vi 10/13/2006 2:01 PM Page vi Contents 3.2.4 Schemes of industrial plants 3.2.5 Industrial safety and environmental protection operational safety 3.2.6 Production control 3.2.7 Performance characteristics and ways of improvement 3.3 Hydrogen–Ammonia and Hydrogen–Amine Systems 3.3.1 Preliminary remarks 3.3.2 Heavy water production by isotope exchange in hydrogen–ammonia systems 3.3.3 Hydrogen–amine system utilization for deuterium enrichment 3.4 Water–Hydrogen System 3.4.1 Historical review 3.4.2 Isotope equilibrium 3.4.3 Hydrophobic catalysts of the isotope exchange process 3.4.4 Types and mass-transfer characteristics of contactors for multistage isotope exchange 3.4.5 Utilization of isotope exchange in water–hydrogen system for hydrogen isotope separation References 117 121 126 127 134 134 135 141 146 146 148 151 153 160 168 Isotope Separation in Systems with Gas and Solid Phases 4.1 Isotope Equilibrium 4.1.1 Chemical isotope exchange reactions 4.1.2 Phase isotope exchange 4.2 Kinetics of Isotope Exchange and Mass Transfer in Separation Columns 4.2.1 Reactions of chemical isotope exchange 4.2.2 Phase isotope exchange 4.3 Counter-Current Isotope Separation Processes 4.3.1 Chromatographic separation 4.3.2 Continuous counter-current separation processes 4.4 Application of the solid-phase systems for the separation of tritiumcontaining hydrogen isotope systems References 175 175 175 181 186 186 190 195 195 199 Carbon Isotope Separation 5.1 Carbon Isotope Separation by Rectification 5.1.1 Isotope effect in the phase isotope exchange and the properties of main operating substances 5.1.2 Carbon oxide (II) cryogenic rectification 5.1.3 Methane rectification 5.2 Cabon Isotope Separation by Chemical Exchange Method 5.2.1 Isotope equilibrium 5.2.2 Cyanhydrine and complex methods of carbon isotope separation 5.2.3 Carbamate method 5.2.4 Comparative economic analysis of carbon isotope separation techniques References 217 217 206 212 217 218 232 236 236 240 240 242 244 Else_SIBE-ANDREEV_contents.qxd 10/13/2006 2:01 PM Page vii Contents vii Nitrogen Isotope Separation 6.1 Nitrogen Isotope Separation by Rectification 6.1.1 Isotope effect and properties of operating substances 6.1.2 Nitrogen isotope separation by NO rectification 6.2 Nitrogen Isotope Separation by Chemical Isotope Exchange 6.2.1 Isotope effect in the chemical exchange reactions 6.2.2 Comparison of isotope effects in chemical and phase exchange 6.2.3 Main production technologies 6.2.4 Ammonium technique of nitrogen isotope separation 6.2.5 Nitrox technique of nitrogen isotope separation 6.2.6 Nitrogen isotope separation by ion exchange 6.3 Comparison of Nitrogen Isotope Separation Techniques 6.4 Large-Scale Production Characteristics References 247 247 247 249 251 251 255 255 257 260 268 268 270 273 Oxygen Isotope Separation 7.1 Oxygen Isotope Separation by Rectification 7.1.1 Isotope effect and properties of operating substances 7.1.2 Heavy oxygen isotope production by water rectification 18 7.1.3 O concentrating by molecular oxygen cryogenic rectification 7.1.4 NO cryogenic rectification 7.2 Oxygen Isotope Separation by Chemical Exchange Method 7.2.1 Separation factor and operating systems 7.2.2 Characteristic properties of separation processes References 275 275 275 277 284 287 290 290 293 296 Subject Index 299 This page intentionally left blank Else_SIBE-ANDREEV_PREFACE.qxd 10/10/2006 5:24 PM Page ix Preface In the 1940s and 1950s, the isotopes of light elements attracted the attention of scientists in the development of nuclear and thermonuclear weapons This is why enrichment and extraction of such isotopes as 2H (deuterium), 3H (tritium), 6Li, and 10B were industrially mastered first In the 1960s, the peaceful use of nuclear energy, development of new nuclear fuels, and wide application of labelled atoms in various fields of human activities, were favourable for implementing industrial methods of nitrogen, oxygen, and carbon isotope separation In recent years, the demand for isotope products used in nuclear medicine has increased sharply A significant demand relates to the isotopes of biogenic elements (hydrogen, carbon, nitrogen, oxygen) According to the forecasts presented in the monograph Isotopes: Properties, Production, Application edited by Yu V Baranov (Moscow, IzdAT, 2000, 704 pp.), it is expected that in the coming years demand will increase dramatically for 18O required for the producion of 18F used in positron emission tomography, and an increasing use of the isotope breath test leading to a steep rise in demand for 13C and 14C isotopes The use of radiogenic 3He in magnetic resonance spectroscopy will spur the production of the radioactive hydrogen isotope tritium The above-mentioned monograph discusses all spectrum of problems associated with the technology and application of isotopes, with emphasis placed on the physical methods of separation The necessity of writing the present book stemmed from two facts First, the last monograph devoted to the problem of the separation of stable isotopes of light elements, Separation of Stable Isotopes by Physical–Chemical Methods by B.M Andreev, Ya.D Zelvenskii, and S.G Katalnikov (Moscow, Energoatomizdat), was published in 1982: in the past 20 years new data on, and novel technologies of, isotope separation processes for these elements have been developed Secondly, we considered it necessary to more comprehensively describe physical–chemical isotope separation methods for biogenic elements allowing for the development of high-capacity and efficient industrial-scale plants The book reflects the present state of research and development, and summarizes both international and Russian experience in the field of separation of isotopes of biogenic elements Along with materials gathered by other scientists, the monograph presents the results of practical work done with the participation of the authors B.M Andreev E.P Magomedbekov A.A Raitman M.B Pozenkevich Yu.A Sakharovsky A.V Khoroshilov ix Else_SIBE-ANDREEV_ch007.qxd 290 11/16/2006 4:09 PM Page 290 Oxygen Isotope Separation between separation stages of the cascade enrichment section, on the concentrations of 15N and 18O in the product withdrawal flow is studied by calculation for a four-stage cascade of which the parameters correspond to those of the NIISI cascade The studies demonstrate that with the use of one or two exchange stages it is possible to increase the 15N concentration to 90at.%, with the 18O concentration remaining not lower than 90at.% An alternative solution can consist of the development of a more complex double cascade, i.e an auxiliary separation stage fed by the withdrawal flow of the NIISI cascade High separation-factor values attained in the NO rectification are still attracting the attention of production engineers despite serious problems associated with this process Figure 7.6 NO cryogenic rectification column [28]: A, feed inlet; W, NO outlet; EA, NO emergency discharge; PWP, roughing-down pump; PD, diffusion pump; C, condenser; C1, column; T1–T3, temperature sensors; M, jacket; B, still; IE, electric heating unit; SN1, SN2, level gauges; PP, sampling; MPD1, MPD2 – differential pressure gauge Else_SIBE-ANDREEV_ch007.qxd 7.2 11/16/2006 4:09 PM Page 291 Oxygen Isotope Separation by Chemical Exchange Method 291 realization A new pilot plant for NO cryogenic rectification, for example, was recently developed at National Institute for Research and Development of Isotopic and Molecular Technologies in Cluj-Napoka, Romania [28] The column C1 (see Figure 7.6), of 7.1m height and 16mm diameter, is filled with Helipack packing material of which the elements are 1.8mm ϫ 1.8mm ϫ 0.2mm in size The still B, with a volume of 100ml, has a built-in electric heater with a maximum power of 150W To ensure adiabaticity, the column is placed in a vacuum jacket M evacuated to a residual pressure of ϫ 10Ϫ5 Torr The plant is completed with a double-chamber condenser C As an intermediate cooling agent, molecular oxygen is used (similar to the Los Alamos laboratory [29]) The column operates at atmospheric pressure As the NO source flow (similar to the NIISI plant [16, 25]) the flow of nitric oxides issuing from the plant was used for nitrogen isotope separation by the Nitrox method and passed through a special system for the purification to a NO content of 99.99% The plant was developed for research purposes, and at a reflux density of 1.2ml/(cm2иmin) the HETP measured value was 7.8cm [28] which is almost threefold that for a column of a similar diameter of the NIISI plant 7.2 7.2.1 OXYGEN ISOTOPE SEPARATION BY CHEMICAL EXCHANGE METHOD Separation factor and operating systems The effective single-stage separation factor values for oxygen isotope separation in operating systems employed in chemical isotope exchange are presented in Table 7.3 [3, 30–34] From the data given in Table 7.3 it can be seen that the highest separation factor values are observed in the CO2 (gas) Ϫ H2O (lq) system ( Ϸ 1.042 at T ϭ 298K) The isotope effect in the system is commensurate with the oxygen isotope separation factor in NO rectification (Table 7.1) The NO, NO2 (gas) Ϫ HNO3 (aq sol) system has a far lower separation factor value compared with the isotope effect in nitric oxide (II) low-temperature rectification For the nitric acid – nitric oxide technique, for one, the value (6.2M HNO3; 298K) is half as great In sulfur dioxide-water exchange, the enrichment factor is about 2.5 times smaller than that in the NO low-temperature rectification Notice that for all systems (methods) under consideration, the heavy oxygen isotope 18O is concentrated in the gas phase By this time, only two oxygen isotope separation methods (initial concentration region) have found practical use They are: chemical isotope exchange between nitric oxides and nitric acid aqueous solution (or the nitric acid – nitric oxide isotope separation method) [35, 36]; and the carbamate isotope separation method [37, 38] It should be pointed out that both processes are used first of all for concentrating other isotopes, with the former for nitrogen isotope separation (chapter 6), and the latter for carbon isotope separation (chapter 5) Despite a small isotope effect, the carbamate system draws attention by the thermal flow reflux method Isotope effect in oxygen isotope separation by the chemical exchange method (at 0.1 MPa pressure) Method Operating system Basic isotope exchange reaction(s) CO2 (gas) – H2O (lq) C 16O16O (gas) ϩ 2H218O (lq) C 16O18O (gas) ϩ H216O (lq) 278 298 313 333 353 373 1.0465 1.0424 1.0392 1.0349 1.0320 1.0292 Nitric acid – nitric oxides NO, NO2 (gas) – HNO3 (sol, aq) 16 18 16 16 18 18 R- n-butyl (-C4H9); solvent – octane (C8H18) a b 1.015 [31] C16O16O (gas) ϩ R2NC16O18OϪ (sol, org) R2NCOOϪb(sol, org) Component concentration in solution R2NCOOϪ, carbamate-anion S 16O18O (gas) ϩ H216O (lq) 1.018 C16O18O (gas) ϩ R2NC16O16OϪ (sol, org) 294 293 1.016 2M [32] 1.013 [33, 34] Oxygen Isotope Separation S 16O16O (gas) ϩ H218O (lq) CO2 (gas) – Carbamate SO2 (gas) – H2O (lq) 8.0M 9.7M 298 H216O(lq) 1.020 Page 292 N O(gas), N O O(gas) ϩ 16 [30] 1.028 6.2M 16 N O(gas), N O O(gas) ϩ 2H2 O(lq) 16 18 Sulfite 4.1M N O(gas), N O O(gas) ϩ HN O3 (sol, aq); 18 4:09 PM N 16O(gas), N16O16O(gas) ϩ 2HN 16O218O (sol, aq) Reference 11/16/2006 Carbon dioxide Conditions T, K Ca Else_SIBE-ANDREEV_ch007.qxd 292 Table 7.3 Else_SIBE-ANDREEV_ch007.qxd 7.2 11/16/2006 4:09 PM Page 293 Oxygen Isotope Separation by Chemical Exchange Method 293 In terms of the organization of the isotope separation process, knowledge of the separation factor must be supplemented with information on the availability and quality of source materials, on kinetics and mass exchange, on the flow conversion completeness, as well with other knowledge that makes it possible to more reasonably speak about technological applicability, advantages, and drawbacks of one or other isotope separation method 7.2.2 Characteristic properties of separation processes CO2 (gas) – H2O (lq) system The CO2 (gas) – H2O (lq) system (carbon dioxide method) is the most favorable in respect of the chemical properties of its compounds The required upper flow conversion is performed chemically on the basis of the methanization reaction (7.7) proceeding due to carbon dioxide reduction by hydrogen CO2 ϩ H CH ϩ H O (7.7) The process is performed on a nickel catalyst at a temperature of 400°C in two stages with intermediate condensation of water vapor [39] The process feature is that it requires close control over oxygen-containing admixtures in hydrogen to avoid isotopic dilution of the product (H218O) It is also necessary to perform a thorough dewatering of methane to ensure against 18O losses The main drawbacks of this method are high hydrogen consumption (4mol per mol of CO2 by stoichiometry only) and a very low mass exchange rate limited by the CO2 hydration In a column of 25mm diameter packed with stainless-steel coils at a relatively high pressure (1.46MPa), for example, HETP was equal to 7.68m at indoor temperature [39] A study on the conditions for the mass exchange efficiency increase, performed in MUCTR, demonstrated that HETP can be reduced to 6–10cm through the use of activating additives (the experiments were performed in a column of 20mm diameter packed with trihedral wire coils of 1.5mm ϫ 2.0mm size), such as monoethanolamine together with sodium selenite at a temperature of over 50°C and pressure greater than 1MPa [40, 41] Nevertheless, despite favorable (from the mass exchange standpoint) results, a practical realization of the conditions found during the study is questionable The problem of the circulation of additives catalyzing the isotope exchange is very difficult from the technological point of view The removal of monoethanolamine, and especially selenite, from the water waste flow followed by their introduction into H218O (at the column upper end) is difficult to realize SO2(gas) Ϫ H2O(lq) system The sulfur dioxide – water system is characterized by the absence of kinetic problems in the exchange of oxygen atoms But the sulfite method of realization (Table 7.3) is conditioned by the flow conversion problem Else_SIBE-ANDREEV_ch007.qxd 11/16/2006 4:09 PM Page 294 294 Oxygen Isotope Separation For the organization of flow conversion, it suggested to reducing SO2 by sulfuretted hydrogen to water by SO2 ϩ H S H O ϩ 3S, (7.8) which proceeds readily in the presence of water vapor For the complete reduction of sulfur dioxide, however, a large excess of sulfuretted hydrogen is required (H2S:SO2 ϭ 2.2:1) Owing to possible water losses in this case, it is unlikely that the process can be used for the flow reflux for separation of oxygen isotopes NO, NO2 (gas) Ϫ HNO3 (aq, sol) system By now, only two chemical isotope exchange processes have been realized (experimentally) for oxygen isotope production These are NO, NO2 Ϫ HNO3, and carbamate CHEX methods [35–37] The former is based on the isotope exchange reaction between nitric oxides and the aqueous solution of nitric acid (Table 7.3) The isotope exchange rate in this system is fairly high: for laboratory-scale columns, HETP accounts for some centimeters [36, 42] (according to E Oziashvili and co-workers [42], HETP ϭ 5.6cm) This method is distinguished by the possibility of integration with a plant for nitrogen isotope separation by the Nitrox method (see chapter 6), both through the gas phase and, probably, through the liquid phase First and foremost, it allows eliminatation of the problem of the NO source in the 18O concentrating (similar to nitric oxide cryogenic rectification, see section 7.1.3) Such an integrated engineering solution is exemplified by the plant for 15N and 18O production developed by D Axente and co-workers [36] at the National Institute for Research and Development of Isotopic and Molecular Technologies in Cluj-Napoka, Romania, for which the scheme is shown in Figure 7.7 The left-hand side of Figure 7.7 (2, 3, 4) displays a two-stage cascade for 15N concentrating linked through the NO flow (column head, purifier 5, column bottom) with a two-stage cascade (columns 6, 13) for 18O concentrating From the point of view of isotope separation technology with the chemical exchange method, of interest is the solution of the flow conversion problem with respect to 18O (Figure 7.7, columns 6, 13 head) Since the liquid phase includes (generally) two oxygencontaining compounds, H2O and HNO3, it is necessary to obtain these from NO without introducing oxygen compounds from outside This rather complicated problem can be solved by partly decomposing N18O to N2 and 18 O2 molecules either by electric discharge (7, 14 in Figure 7.7) or at the Pt-catalyst at a temperature of over 700°C, as reported by D Axente and co-workers [36] After that, N18O is oxidized by oxygen (18O2) with the formation of N18O2 The obtained nitrogen oxide (IV) is then absorbed by water (H218O) (8, 15), formed from part of the N18O2 through the reaction with hydrogen over chrome–nickel catalyst at a temperature of 750–800°C [42] Formed in the absorber, the HN18O3 solution in the H218O is supplied to the isotope exchange columns 6, 13 as a reflux, and N2 is withdrawn from the plant together with unreacted hydrogen To absorb water vapor contained in N2 during the production of concentrated 18O, it is necessary to use the sorption of water vapor over zeolites (12, 19 in Figure 7.7), because, even Else_SIBE-ANDREEV_ch007.qxd 7.2 11/16/2006 4:09 PM Page 295 Oxygen Isotope Separation by Chemical Exchange Method 295 Figure 7.7 Scheme of nitrogen and oxygen isotope separation by the nitric acid – nitric oxides method at National Institute for Research and Development of Isotopic and Molecular Technologies in Cluj-Napoka, Romania [36]: 1, 2, 15N concentration columns of first and second stages, respectively; 3, 4, HNO3 reduction reactor; 5, packed column for NO purification; 6, 13, 18 O concentrating columns; 7, 14, reactor for NO decomposition by electrical discharge; 8, 15, absorber; 9, 16, reaction mixture preheater; 10, 17, H2O production reactor; 11, 18, heat exchanger; 12, 19, zeolite adsorber if the condenser is cooled to 0°C, the content of water vapor in the gas is Ϸ ϫ 10Ϫ4 g/l, as against the permissible value accounting for ϫ 10Ϫ6 g/l for the production of 70at.% 18 O [42] CO2 (gas) Ϫ R2NCO2Ϫ (sol, org) system Oxygen isotope separation by the carbamate method provides the second example of the application of chemical exchange, but with more attractive thermal methods of flow reflux [33, 34] (Table 7.3) In this case the flow conversion is performed through the reaction equilibrium displacement with heat application or rejection heating heating 2R NH (sol,org) ϩ CO2(gas) ᎏ R NCOONR 2(sol,org) ᎏ R NCOOϪ (sol,org) cooling ϩ R NHϩ 2(sol,org) cooling (7.9) Else_SIBE-ANDREEV_ch007.qxd 11/16/2006 4:09 PM Page 296 296 Oxygen Isotope Separation For a laboratory-scale column, with the use, for example, of 2M n-DBA solution in triethylamine, at a temperature of 25°C, a specific gas flow rate of 0.06–0.24mol CO2/(cm2иh), and with Helipack 3013 packing, HETP was equal to about 2–8cm [36] Somewhat higher HETP values were obtained for spiral-prismatic packing with an element size of 2.3mm ϫ 2.3mm ϫ 0.2mm [36] Enrichment with 18O of more than 200-fold was obtained at an enlarged pilot plant with a 40m packed column (51mm internal diameter) This was intended primarily for 13C concentrating, with the use of the carbon dioxide-n-DBA carbamate in octane system, simultaneously with 13C concentrating [37] In addition to the interest in this isotope, the result is capable of significantly improving the carbamate method’s economic performance for carbon isotope separation [43] (chapter 5) Besides, the process also allows solution of the problem of initial 18O concentration for further enrichment with the use of combined process schemes [44], i.e in combination, for example, with the gas-centrifugal method [45] or with sorbtion on zeolites [24] REFERENCES K Clusius, K Schleich, Helv Chim Acta., 1958, 41, 6, 1342 K Clusius, K Schleich, M Vechi, Helv Chim Acta., 1959, 42, 6, 2654 T F Johns, In: Proc Intern Symp on Isotope Separation, Amsterdam, North-Holl and Pub Co., 1958, 74 A E Kovalenko author’s abstract, Ph.D thesis, Mendeleev University of Chemical Technology, 1971, 24 A E Kovalenko, Ya D Zelvensky, Isotopenpraxis, 1969, 5, 1, 20 E Ancona, G Boato, G Casanova Nuovo Cimento, 1962, 23, 1041 K Clusius, F Endtinger, K Schleich, Helv Chim Acta, 1961, 44, 98 A Van Hook, J Phys Chem., 1968, 72, 234 S Shapiro, F Steckel, Trans Farad Soc., 1967, 63, 4, 883 10 O V Uvarov, N M Sokolov, N M Zhavoronkov, Zhurn Phiz Khimii, 1962, 36, 2699 11 O V Uvarov, Production and Properties of Heavy-Oxygen Water, L Ya Karpov NIPhKhI, 1963, 44 12 D Jickli, D F Staschewski, Chem Soc Farad Soc., 1977, 72, 1505 13 D Staschevski, Chem Technol., 1975, 4, 8, 269 14 I Dostrovsky, A Raviv, Proc Int Symp Isotope Separation, Amsterdam, McGraw Hill Book Co., 1958, 336 15 L Streltsov, N Zhavoronkov, T Gumeniuk et al., Khim Prom., 1974, 3, 221 16 P Ya Asatiani et al., In: Stable Isotopes in the Life Sciences, IAEA, Vienna, 1977, 75 17 D Staschewski, In: Stable Isotopes in the Life Sciences, IAEA, Vienna, 1977, 85 18 A S Polevoy, M N Polyansky, In: Proc 2nd All-Russian Conference on Physical-Chemical Processes in Selection of Atoms and Molecules, TsNIIatominform, 1997, 111 19 A O Edmunds, I M Lockhart, In: Isotope Rations as Pollutant Source and Behav Indic., IAEA, Vienna, 1975, 229 20 W R Daniels, A O Edmunds, I M Lockhart, In: Stable Isotopes in the Life Sciences, IAEA, Vienna, 1977, 21 21 A E Kovalenko, Ya D Zelvensky, E.S Vaynerman, Atomnaya Energiya, 1969, 27, 541 22 Ya D Zelvensky, Isotope Separation by Cryogenic Ractification, Mendeleev University of Chemical Technology of Russia, 1998, 208 Else_SIBE-ANDREEV_ch007.qxd References 11/16/2006 4:09 PM Page 297 297 23 Ya D Zelvensky, Khim Prom., 1999, 4, 32 24 B M Andreev, E P Magomedbekov, I L Selivanenko, In: Proc 2nd All-Russian Conference on Physical-Chemical Processes in Selection of Atoms and Molecules, TsNIIatominform, 1997, 123 25 G Ya Asatiani, candidate of technological science thesis, Mendeleev Institute of Chemical Technology, 1981, 20 26 R I Sidenko, G A Sulaberidze, V A Tchuzhinov, V M Vetsko, In: Proc Mendeleev Institute of Chemical Technology, 1989, 156, 57 27 R I Sidenko, G A Sulaberidze, V A Tchuzhinov, V M Vetsko, Atomnaya Energiya, 1990, 69, 4, 255 28 M G Gligan, A Radoi, S Dronca, C Bidian et al., Revista de Chimie, 1997, 48, 335 29 D E Armstrong, B B McInteer, T R Mills, J G Montoya, In: Stable Isotopes Proc Third Intern Conf., New York, Academic Press, 1979, 175 30 D Staschewski, Ber Bunsenges Physik Chem., 1964, 68, 5, 454 31 S C Saxena, T I Taylor, J Phys Chem., 1962, 66, 8, 1480 32 L L Broun, J S Drury, J Phys Chem., 1959, 63, 11, 1885 33 J P Agraval, Separation Sci., 1971, 6, 6, 819 34 J P Agraval, Separation Sci., 1971, 6, 6, 831 35 M Abrudean, D Axente, S Bâldea, Isotopenpraxis, 1981, 17, 11, 377 36 D Axente, A Bâldea, M Abbrudean, In: Proc Int Symp on Isotope Separation and Chemical Exchange Uranium Enrichment (Bull Res Lab for Nuclear Reactors, special issue 1), 1992, 357 37 A S Egiazarov, G V Hatchisvili, T G Abzianidze, In: 5th International Symposium on the Synthesis and Applications of Isotopes and Isotopically Labelled Compounds, Strasbourg, France, June 20–24, 1994, P028, p 146 38 T I Taylor, J Chim Phys Phys Chim Biol., 1963, 60, 1–2, 157 39 W T Boyd, R R White, Ind Eng Chem., 1952, 44, 9, 2202 40 B M Andreev, T D Gumeniuk, Ya D Zelvensky, In: Proc Mendeleev Inst Chem Technol., 1970, LXVII, 100 41 B M Andreev, T D Gumeniuk, Ya D Zelvensky, A M Meretsky, Isotopenpraxis, 1971, 7, 5, 180 42 E D Oziashvili, Yu V Nikolaev, N F Myasoedov, Rep Acad Sci Georgian SSR, 1962, XXIX, 3, 289 43 A Kitamoto, K Takeshita, In: Proceedings of the International Symposium on Isotope Separation and Chemical Exchange Uranium Enrichment (Bull Res Lab for Nuclear Reactors, special issue 1), 1992, p 376 44 A V Khoroshilov, In: Tenth Symposium on Separation Science and Tehnology for Energy Application, Gatlinburg, TN, October 20–24, 1997, 76 45 Yu V Petrov et al., Patent RU 2092234, C1, 10.10, Inventions, 1997, 28, 199 This page intentionally left blank Else_SIBE-ANDREEV_Subjectind.qxd 11/14/2006 5:42 PM Page 299 Subject Index 139–140, 146, 153–154, 159–160, 164, 167, 207, 259, 294 Cohen equation, 20 cold column, 74, 76–78, 82–83, 85–88, 94, 96–97, 107–112, 115–120, 126, 129–134, 139, 143, 145, 166 combined electrolysis and catalytic exchange (CECE), 147,160,163−167 complicated isotope exchange, concentration column, 19–22, 27–28, 59–60, 278, 295 condenser, 42, 47, 49, 59, 61, 63, 65–66, 68, 136, 222–225, 231–233, 236, 249–250, 279, 285–286, 288–291, 295 counter-current column, 8, 12, 35, 39, 59–60 movement, 13, 34, 199–202, 206, 232 separation, 7, 12, 73, 196, 198, 200–201, 206–207, 209 critical temperature, 45, 50, 217, 247, 275–276 cryogenic rectification, 50, 52–70, 133, 146, 162–163, 184, 207–209, 211, 218, 220–222, 224, 226, 228, 230, 232–233, 249, 251, 266, 269, 277, 284, 286–291, 294 CTEX, 59–60, 66, 147, 153, 207–209 cyanhydrine, 236–237, 240, 243 cyanide, 144, 236–238 absorption, 47, 115, 127, 236−238, 261, 271, 289 ammonia, 45–50, 53–54, 78, 115, 134–142, 144–146, 247–248, 250–252, 255, 257, 259, 261, 269–272 complex, 270–271 rectification, 45–48, 136, 138, 140, 269–271 ammonium, 251–252, 254–255, 257–260, 268–272 carbonate, 251 method, 258, 268–269, 271 average separation factor, 210, 282 bicarbonate, 237–238 binary isotopic mixture, 1, 164, 181–182 boiling point, 42, 45–46, 50–51, 217–218, 247, 249, 275–276 bubble cup tray, 108–109, 128 carbamate, 237–238, 240–243, 291–292, 294–296 method, 237, 240–243, 295–296 carbon dioxide, 50, 121, 218, 236, 241, 283, 293, 296 carbon isotope separation, 217–220, 222, 228, 233–234, 236–238, 240–243, 291, 296 carbon isotopes, 228, 235, 243 carbon monoxide, 161, 185, 217, 275 cascade of separation columns, 26 catalytic activity, 144, 151 catalytic isotope exchange (CTEX), 55–57, 59–61, 68, 70, 152, 207, 231 chemical exchange, 7, 73, 146, 148, 236–237, 241, 243, 248, 251–252, 255, 257, 266, 268–272, 289, 292, 294–295 distillation, 47 plant, 47 chemical isotope exchange (CHEX), 1, 12, 146, 158, 167, 175, 181, 186, 203, 211, 237–239, 244, 249, 255, 257, 268, 271, 290–291, 294 CHEX, 1–4, 6–12, 47, 103, 136–137, density, 10, 30, 33, 39, 109, 128, 217, 241, 247, 275–276, 290 depletion column, 14, 19–22, 234, 278 section, 14–15, 18–19, 48–49, 52, 63, 69, 74, 131, 135–136, 138–140, 161, 199–201, 220–221, 224–226, 228–229, 249–250, 278, 280, 288–289 deuterium, 41–42, 45–62, 64–68, 75, 94, 99–100, 117, 119, 121, 126, 131, 133, 135–141, 146–151, 156–158, 163–164, 166, 176, 180, 182, 196, 198, 203, 205–209, 277, 281–282 299 Else_SIBE-ANDREEV_Subjectind.qxd 11/14/2006 300 deuterium-protium, 41, 45, 67, 75, 94, 147− 151, 156−157, 163−164, 182, 198, 209, 277 deuterium-tritium, 64 differential separation factor, diffusion, 6–8, 10, 12, 37–38, 99–100, 104–106, 142, 145, 152, 187–190, 193, 196, 203, 242, 257, 259, 279, 285, 291 coefficient, 8, 10, 12, 37, 104–105, 196 dioxide complex, 251, 255, 257 distillation, 47, 69, 161, 218–219, 248 column, 47 plant, 47 Dixon rings, 30–31, 43, 56, 228, 234–235, 281 effective separation factor, 2–4, 88, 98–99, 134, 141, 257, 260, 290 electrochemical cell, 159 electrolysis, 54, 56, 131, 137, 146–147, 163, 167, 281–282 electrolysis and exchange (ELEX), 147 electrolyzer, 60–61, 161–164, 166–167 enrichment, 1, 46, 48, 55–57, 74, 77, 82, 92, 119, 130–132, 135–136, 138–141, 161, 163, 182, 185, 196–198, 200–201, 208, 211, 217, 221–226, 229, 232, 234, 237, 239, 242, 250–251, 255–256, 263, 266, 272, 275–276, 278, 280, 283, 288–290, 296 column, 135, 139, 234, 250 factor, 1, 217, 237, 239, 251, 255–256, 276, 290 enthalpy, 4, 112–115, 178 equilibrium constant, 1–2, 4, 41, 45–46, 51, 55, 57, 94, 102, 136, 149–150, 175, 178, 184 evaporator, 46, 48, 59, 65–66, 136–137, 223–227, 232, 250–251, 279, 288–289 exchange reactor, 231 extraction degree, 15–18, 20, 23, 28, 45–46, 52–53, 74, 78–80, 92, 96, 117, 129–131, 139–141, 223, 228, 289 Fenske equation, 19, 21 flow conversion, 13, 22, 26–27, 73, 75–76, 92, 111, 135, 147, 158, 160–161, 163, 167, 198–200, 202, 237, 240–242, 255, 257–259, 261, 265, 269, 271–272, 289, 293–295 5:42 PM Page 300 Subject Index conversion unit, 13, 22, 27, 147, 158, 160–161, 163, 167, 202, 240–242, 271–272 ratio, 9–10, 14–15, 17–20, 34, 77, 81–82, 90 reflux, 12–13, 24, 255, 257, 259–260, 262, 265–272, 291, 294–295 reflux unit, 13, 266, 271–272 gaseous phase, 2–4, 9, 59–61 gas−liquid, 7, 9−10, 12, 34, 73, 87, 93, 100, 112, 154, 236, 251 gas–solid, 199 half-exchange time, 7, 240 heat consumption, 76, 97, 127–128 exchanger, 55, 57–58, 111–112, 114–117, 119, 121, 127–128, 133, 207–208, 229, 231–232, 272, 287, 295 of evaporation, 217, 247, 275–276 recovery, 93, 111, 115, 119–120, 128, 133 heavy carbon isotope, 217, 221, 241 isotope, 2–4, 8–9, 60–61, 72–75, 80, 94, 99–100, 129, 136, 176–178, 180, 182, 188, 190, 193, 196, 198–199, 201, 204, 247–248, 250, 278, 280–281, 283, 289 oxygen water, 279−281, 283−284 water, 41–45, 48, 50, 52–62, 64, 70, 122, 127–129, 131–135, 137, 139, 141, 144, 146, 160, 164, 206, 208, 277, 281–283 height equivalent for the theoretical plate of separation (HETP), 9−10, 12, 18−19, 38, 43, 49, 56, 122, 200, 202−205, 210, 220, 222−223, 226, 228, 230, 235, 237, 240−241, 250, 259−262, 264−266, 268, 278, 285, 289−290, 293−294, 296, height of the transfer unit (HTU), 9−12, 38−39, 103, 105−106, 108, 157, 189−196, 235−236 heterogeneous isotope exchange, HMEX reaction, 182, 185, 209, 224, 249, 284, 289 holdup, 23, 26, 35–36, 42, 63, 65–68, 70, 91, 93, 131, 133, 158, 167, 208, 210, 223, 240 homomolecular isotope exchange (HMEX), 51, 181, 269, 284 hot column, 74, 76–77, 79, 82–83, 85–86, 88, 92, 94–97, 99, 107–109, 111–112, 115–122, 126–134, 138–141, 143–145, 147, 166 Else_SIBE-ANDREEV_Subjectind.qxd 11/14/2006 5:42 PM Page 301 Subject Index hydraulic resistance, 34–36, 42, 48–49, 53, 108–110, 112, 115, 128, 133, 138, 154, 157–158, 188, 235–236 hydrogen−amine system, 134−135, 141 hydrogen−ammonia system, 115, 134−135, 141, 146 hydrophilic, 154–155, 158–160 hydrophobic catalyst, 59–61, 147, 151, 153–154, 159, 166 properties, 147, 151 hydrogen isotope exchange, 6, 11, 46, 107, 147, 153, 162, 166, 175, 188 isotope separation, 10, 24, 41, 53, 62, 73, 80, 95, 100, 145, 147, 160, 167, 175, 188, 197–198, 200, 209 isotopes, 5, 41, 51–52, 59, 62–63, 149, 162, 175–176, 178, 181, 186, 196–197 rectification, 50–53, 56, 167, 184 sulphide, 3, 75, 86, 88, 94−97, 100−104, 112−118, 128−131, 135, 146 sulphidous medhod, 76, 93, 99, 108−111, 117, 119−121, 123−127, 129, 132−133 hypersorption, 190, 192, 195–196, 200, 207, 209, 211 ion exchange, 69, 161, 253, 268 isotope effect, 1, 4–7, 9, 11–12, 89, 99, 107, 175–178, 181–185, 190, 217–219, 236–238, 247–248, 251–252, 255, 275–277, 290–292 equilibrium, 7, 12, 62, 93–94, 136, 148, 175, 182, 236 exchange, 1–3, 6–8, 10–12, 41, 45–51, 54–57, 59–61, 63, 66–70, 72–74, 76, 78, 83, 86, 93–94, 99–103, 105–108, 112, 114, 128–130, 135–144, 146–147, 149, 151–153, 156–158, 160–167, 175–176, 178, 181–182, 184, 186–188, 190, 192, 196–197, 201, 203, 207, 211, 217, 220–221, 228, 230–231, 237–240, 242, 248–249, 251–252, 254–255, 257–260, 268–269, 271–272, 284, 289–294 exchange rate, 7–8, 101–103, 141–144, 175, 186–187, 197, 257, 294 exchange reaction, 1–2, 6–7, 45, 47, 49, 74, 301 93–94, 99, 102, 108, 136, 142, 149, 151, 175–176, 178, 181, 187, 203, 207, 211, 220–221, 237–238, 252, 254, 260, 292, 294 mass-transfer, mass-transport, separation, 1, 10, 12, 24, 26, 29–30, 41, 45, 53, 62, 65, 67–70, 73, 75, 80, 86, 95, 100–101, 145, 147, 156, 160, 162, 167, 175, 181, 188, 195–200, 202–203, 206, 209–211, 217–220, 222, 228, 233–234, 236–238, 240–243, 247–249, 251–252, 255–260, 262, 266, 268–270, 272–273, 275–278, 284–288, 290–296 isotopic composition, 14, 52, 78, 101, 105, 126, 132, 165, 209, 220, 233, 271 mixture, 1, 106, 150–151, 157, 164, 181–182, 184 ITER, 65, 67–68, 160, 167, 209 JET, 210 kinetic isotope exchange, 6−7, 186−187 kittel perforated plates, 49, 107 liquid density, 10, 33, 217 liquid−gas systems, 2, 75, 237, 268 liquid phase catalytic exchange (LPCE), 59, 147, 162 liquid−solid, 251 liquid−vapor equilibrium, 5, 52, 64, 217 low-temperature, 41, 131, 217, 247, 249, 255, 270–272, 287, 290 rectification, 131, 217, 255, 270–272, 287, 290 mass-transfer, 8–10, 12, 21, 37, 39, 56, 81, 89, 100–101, 104–105, 107–111, 114, 121, 134, 137, 139, 142, 145, 152–160, 189, 193, 235–237, 262 coefficient, 8–10, 21, 56, 81, 101, 155, 158–160, 189, 193, 235 efficiency, 104–105, 107–108, 110, 155–156 process, 37, 100, 114, 142 resistance, 8–10, 107 volume factor, 142, 152, 235, 262 melting point, 217–218, 247, 275–276 membrane, 154, 159–160 membrane-type contactors (MTC), 159 Else_SIBE-ANDREEV_Subjectind.qxd 11/14/2006 5:42 PM 302 metal mesh rings (MMR), 30−31, 35, 228, 234−236, 287 methane, 50, 55, 137, 140–141, 166, 185, 217–219, 226, 233–237, 240, 242, 266, 288–289, 293 rectification, 218, 233–237, 240 methylamine−hydrogen system, 144−145, 148 mole fraction, 87, 97, 122 multistage counter-current separation processes, 12 isotope exchange, 153 nitric oxide, 247–251, 253, 255, 259–262, 266, 269–271, 273, 275, 277, 287–292, 294–295 nitric acid, 46, 161, 249, 251, 253, 257, 259–266, 269, 271–273, 287, 290–292, 294–295 nitrogen−hydrogen mixture (NHM), 50, 54, 135 nitrogen isotope separation, 195, 206, 247–249, 251–252, 255–260, 262, 268–270, 272–273, 275, 290–291, 294 nitrogen isotopes, 195, 202, 204 Nitrox process, 251, 260, 265–266 system, 251, 260 non-withdrawal mode, 19, 21, 25–26, 28, 74, 81–83, 85, 89, 91–93, 201–202, 235 normal boiling point, 42, 45–46, 50–51, 217–218, 247, 275–276 NTP, 15, 17–20, 22, 26, 28, 38, 43, 45, 65–66, 68–70, 81–86, 90–92, 122, 208, 210, 220, 223, 230, 242 NTU, 21–22, 38, 81–84, 91–93, 104, 106, 131 number of theoretical plates, 65–66, 68 of transfer units, 21 operating line, 14–16, 20, 22, 28, 76, 83, 86, 122 substance, 217, 247, 249, 271, 275, 277 system, 22, 133, 145, 236–238, 240, 248, 251, 271, 277, 290, 292 ortho-hydrogen, 51 overall separation degree, 258 oxide complex, 251, 255 Page 302 Subject Index oxygen, 50, 52, 54, 60–61, 121, 137, 144, 164–165, 184–186, 195–196, 202, 204, 212, 218, 220, 224, 226, 240, 249–250, 261, 266, 275–287, 289–295 isotopes, 185–186, 195, 202, 249, 283–284, 294 packing, 10–11, 22, 29–39, 42–45, 48–49, 56–57, 60, 62–63, 68–70, 99, 103–110, 112, 121, 130–131, 133, 154–160, 220–224, 226–228, 230, 232–236, 240–241, 250, 258–260, 262–264, 266, 278, 280–285, 287–290, 296 bed, 33–37, 43–44, 57, 63, 68–70, 108, 112, 131, 160, 224, 228, 230, 232–234, 259, 278, 280–281, 283–285, 289 material, 10, 29–36, 39, 43, 56–57, 60, 62, 69–70, 99, 103, 105–108, 154–155, 158–159, 221, 223–224, 234–235, 240, 250, 258, 263, 280–281, 283–284, 288, 290 type, 35, 37, 156, 222, 230, 235–236 para-hydrogen, 51 pilot module, 226–227 plant, 92, 109–110, 141, 145, 151, 155, 162, 164, 166, 203, 218, 220, 228, 233, 259, 281, 290, 296 phase diagram, 95–96 phase isotope exchange (PHEX), platinum catalyst, 147, 151, 250 protium, 41, 45, 55–58, 64, 67–68, 75, 94, 130–134, 146–151, 156–158, 160, 162–164, 182, 198, 203, 207–209, 211, 277 protium−deuterium system, 148−149, 151, 156 protium−tritium system, 147 power consumption, 42–43, 47–48, 50, 110, 112, 127, 133, 141, 145, 230–231 purification, 50, 52–53, 55–62, 66, 69, 121–122, 127, 129–140, 146, 160–161, 163–165, 167, 200, 207–211, 218, 220, 224–226, 228, 233, 249–250, 285, 288–290, 295 Rayleigh distillation, 218−219, 248 reflux, 12–13, 24, 27, 30, 35, 38–39, 42–45, 47–49, 52–55, 57, 59, 63–66, 68–69, 119, 121, 137, 139, 223–224, 241, 255, 257–260, 262, 265–272, 285–287, 290–291, 294–295 Else_SIBE-ANDREEV_Subjectind.qxd 11/14/2006 5:42 PM Page 303 Subject Index ratio, 63–66, 68–69 unit, 13, 42, 53, 258, 265–266, 271–272 relative concentration, withdrawal, 15, 17, 19, 23, 76, 80, 86, 130, 133, 210 relaxation time, 24, 92 self-diffusion coefficient, 105 separation cascade, 17, 127, 166, 279, 283, 288–289 column, 10, 12–13, 15, 26, 29, 76, 78, 107, 117–118, 122, 128, 131, 157, 186, 197–199, 201, 204–205, 271–272, 285 column plant, 12–13 degree, 17, 19–20, 22–23, 26–28, 49, 76, 80–83, 90–91, 96, 118, 129, 131, 159, 161, 192, 196–198, 202, 206, 237, 258 element, 12–13 factor, 1–6, 10, 15, 24, 41–42, 45–46, 50–53, 56, 73, 78–80, 82, 88–89, 94, 96–101, 129–130, 134–135, 141, 144, 146, 148–149, 175–177, 179–186, 190, 197, 205, 208, 210, 217–218, 220, 228, 236–237, 240, 247–248, 251, 255, 257, 259–260, 268, 275, 277–278, 281–282, 284–287, 290, 293 plant, 15, 26, 73, 131, 133, 147, 157–158, 160–161, 165, 167, 175, 188, 199, 202, 208–209, 234, 241, 266, 285 sieve tray, 107–110, 126, 128, 138–140, 145 single isotope effect, 12 single-stage separation effect, factor, 247, 251, 259–260, 268, 275 solid-state polymeric electrolyte (SPE), 147 spiral-prismatic packing (SPP), 156 steady state, 23–25, 80, 89, 91–93, 127, 200, 202, 204 303 theoretical plate (TP), 12, 92 thermodynamic isotope effect (TDIE), 1, 88 tray type, 109 triple isotopic mixture, 106 tritium, 3, 10, 41, 55–70, 94, 105, 129–133, 146–147, 149–151, 156–158, 160–165, 167, 180, 182, 184, 188, 196, 198, 202–211, 283 extraction, 55–56, 58–62, 70, 129–131, 203 tritium−containing isotope mixture, 10, 150 two-phase system, 1, 12, 255–256 two-temperature cascade, 76, 120 method, 73, 75–76, 78, 83, 86, 92, 129 plant, 72–83, 86–88, 90–92, 96, 109, 111, 115, 117, 121–122, 126, 128–133, 139–140, 159 unsteady state, 23, 91–92, 204 water, 3, 12, 24, 26, 29, 41–50, 52–62, 64, 68–70, 75, 78, 86–88, 93–97, 99–105, 107–135, 137–141, 144–150, 152–156, 158–168, 182, 196, 206–209, 211, 218, 226, 239–240, 249–250, 259, 261–262, 265–266, 268, 271, 275–287, 290, 293–295 water−hydrogen sulphide system, 146 water−hydrogen system, 146 water rectification, 41–45, 68–70, 140, 165, 182, 209, 277, 280–284, 286 water vapor−hydrogen exchange, 146 withdrawal of first kind, 16, 18, 21, 27, 74, 79, 81, 84, 88, 90, 225–226, 278 of second kind, 17–18, 20, 27, 74–76, 79, 81–82, 84, 86, 91, 130, 225–226, 278 This page intentionally left blank ... Page i Separation of Isotopes of Biogenic Elements in Two-phase Systems This page intentionally left blank Else_SIBE-ANDREEV_prelims.qxd 10/10/2006 5:27 PM Page iii Separation of Isotopes of Biogenic. .. assembly of flow inversion Here the main expenses of separation are caused by liquid and gas flow circulation and heating (cooling) The physico-chemical and engineering bases of production of the isotopes. .. problems of separation of isotopes of the other biogenic elements such as carbon, nitrogen, and oxygen Heavy stable isotopes of these elements, 13C, 15 N, 17O, and 18O, are indispensable when studying