Cascade units for neon isotopes production by rectification method

Basics of neon separation into isotopes by distillation method at T = 28 K are discussed. The required numbers of transfer units of the top and bottom column sections at different loads are calculated. The experimental characteristics of packed rectification columns are presented and examples of t...

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Hauptverfasser: Bondarenko, V.L., Simonenko, Yu.M., Diachenko, O.V., Matveyev, E.V.
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Veröffentlicht: Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України 2013
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Zitieren:Cascade units for neon isotopes production by rectification method / V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko, E.V. Matveyev // Физика низких температур. — 2013. — Т. 39, № 5. — С. 617–622. — Бібліогр.: 9 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-118462
record_format dspace
spelling Bondarenko, V.L.
Simonenko, Yu.M.
Diachenko, O.V.
Matveyev, E.V.
2017-05-30T11:53:57Z
2017-05-30T11:53:57Z
2013
Cascade units for neon isotopes production by rectification method / V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko, E.V. Matveyev // Физика низких температур. — 2013. — Т. 39, № 5. — С. 617–622. — Бібліогр.: 9 назв. — англ.
0132-6414
PACS: 51.30.+j
https://nasplib.isofts.kiev.ua/handle/123456789/118462
Basics of neon separation into isotopes by distillation method at T = 28 K are discussed. The required numbers of transfer units of the top and bottom column sections at different loads are calculated. The experimental characteristics of packed rectification columns are presented and examples of the cascade outlined. A scheme of cryogenic circuit based on the high-pressure throttle neon cycle with intermediate nitrogen cooling is presented. The necessity and the technical ability to create the driving difference of pressures between columns of various stages demonstrated.
en
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
Физика низких температур
9th International Conference on Cryocrystals and Quantum Crystals
Cascade units for neon isotopes production by rectification method
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Cascade units for neon isotopes production by rectification method
spellingShingle Cascade units for neon isotopes production by rectification method
Bondarenko, V.L.
Simonenko, Yu.M.
Diachenko, O.V.
Matveyev, E.V.
9th International Conference on Cryocrystals and Quantum Crystals
title_short Cascade units for neon isotopes production by rectification method
title_full Cascade units for neon isotopes production by rectification method
title_fullStr Cascade units for neon isotopes production by rectification method
title_full_unstemmed Cascade units for neon isotopes production by rectification method
title_sort cascade units for neon isotopes production by rectification method
author Bondarenko, V.L.
Simonenko, Yu.M.
Diachenko, O.V.
Matveyev, E.V.
author_facet Bondarenko, V.L.
Simonenko, Yu.M.
Diachenko, O.V.
Matveyev, E.V.
topic 9th International Conference on Cryocrystals and Quantum Crystals
topic_facet 9th International Conference on Cryocrystals and Quantum Crystals
publishDate 2013
language English
container_title Физика низких температур
publisher Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
format Article
description Basics of neon separation into isotopes by distillation method at T = 28 K are discussed. The required numbers of transfer units of the top and bottom column sections at different loads are calculated. The experimental characteristics of packed rectification columns are presented and examples of the cascade outlined. A scheme of cryogenic circuit based on the high-pressure throttle neon cycle with intermediate nitrogen cooling is presented. The necessity and the technical ability to create the driving difference of pressures between columns of various stages demonstrated.
issn 0132-6414
url https://nasplib.isofts.kiev.ua/handle/123456789/118462
citation_txt Cascade units for neon isotopes production by rectification method / V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko, E.V. Matveyev // Физика низких температур. — 2013. — Т. 39, № 5. — С. 617–622. — Бібліогр.: 9 назв. — англ.
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first_indexed 2025-11-24T02:23:15Z
last_indexed 2025-11-24T02:23:15Z
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fulltext © V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko and E.V. Matveyev, 2013 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5, pp. 617–622 Cascade units for neon isotopes production by rectification method V.L. Bondarenko Moscow Bauman State Technical University, 5, 2-d Baumann Str., Moscow 107005, Russia Yu.M. Simonenko Iceblick, Ltd., 29 Pasteur Str., Odessa 65026, Ukraine O.V. Diachenko and E.V. Matveyev Odessa National Academy of Food Technologies, V.S. Martynovsky Educational-Scientific Institute of Refrigeration, Cryotechnologies and Ecoenergy, 1/3 Dvoryanskaya Str., Odessa 65082, Ukraine E-mail: diachenko-ov@yandex.ua Received November 23, 2012 Basics of neon separation into isotopes by distillation method at T = 28 K are discussed. The required num- bers of transfer units of the top and bottom column sections at different loads are calculated. The experimental characteristics of packed rectification columns are presented and examples of the cascade outlined. A scheme of cryogenic circuit based on the high-pressure throttle neon cycle with intermediate nitrogen cooling is presented. The necessity and the technical ability to create the driving difference of pressures between columns of various stages demonstrated. PACS: 51.30.+j Thermodynamic properties, equation of state. Keywords: neon isotopes, rectification, packed rectification columns. 1. Introduction Nearly one hundred years ago A.J. Thomson has deter- mined for the first time existence of stable elements iso- topes 20 Ne and 22 Ne [1]. 21 Ne was discovered in the twen- ties. Neon isotopes are widely used in modern high technologies. 20 Ne + 22 Ne mixtures are object of research of the physicists, who study mechanism of photonuclear reactions. Isotopic anomalies help in disclose secrets of our planetary system formation. In particular, astronomers have found out that 22 Ne monoisotope is produced when some meteorites are heated. At the same time the total con- tent of 21 Ne and 20 Ne doesn't exceed 1% (nearly two or- ders lower than in neon extracted from the Earth atmos- phere). Neon isotopes gas mixture ( 20 Ne + 22 Ne) is an active medium in gyroscopes, the operation of which is based on Szeemann's effect [2]. They are resistant to the mechanical influences and have stable scale factor. Besides navigation, such devices are in demand in different areas of fundamental research in physics. Very perspective is the sphere of application of the rarest of the neon isotope 21 Ne. Physicians believe that its nuclear and physical properties allow using it as an alternative to 3 Не isotope in magnetic resonance imaging diagnostics of lungs ventilation. 2. Neon separation into isotopes by rectification method In 1913 the first mass spectrometer, which was invented a year earlier, was used for separation of neon isotopes samples. Separation of 20 Ne and 22 Ne isotope pair for la- boratory and industrial purposes is also possible by me- thods of thermal diffusion and chromatography [1,3]. Neon is at the limit of application of distillation method, which is considered to be effective at molecular masses less than 20 [4]. Separation coefficient of 20 Ne and 22 Ne isotopes be- tween liquid and vapor phases in equilibrium at tempera- tures 27 K 30 KТ is = 1.040–1.032 [5]. Neverthe- less, the low-temperature rectification is considered to be the most perspective method of neon separation [6]. This statement becomes even more powerful, if one of the target products is 21 Ne. Let's consider the process of the 20 Ne + 22 Ne binary mix- ture separation. Illustratively let’s consider у–x diagram with the reference to the high-boiling isotope. Figure 1(b) shows that the graph is symmetric to the typical diagram, mailto:diachenko-ov@yandex.ua V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko and E.V. Matveyev 618 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 constructed with the reference to the low boiling compo- nent of mixture. This fact allows avoiding unnecessary recalculations of concentration and provides information on the contents of the target product ( 22 Ne) in streams and sections of the column immediately. Table 1 shows the results of calculation of the number of theoretical plates (NTP) for the top and bottom sections of the column. Isotope concentrations of the streams, ac- cepted in calculation, are the following: – initial mixture with х0 = 0.0925 ( 22 Ne natural isotope ratio of 9.25%); – bottom section of the column product хP = 0.9999; – waste stream, removed in the upper part of the co- lumn, хW = 0.015. At such concentrations of the waste flow W we lose 15% of the target product, and the level of extraction is С = 0.85, where 0 0 ( ) ( ) W P P W x x x C x x x . (1) In accordance with the definition of the NTP, it was ac- cepted that liquid and vapor are in equilibrium at each elementary rectification stage. In general case the equation for the upper column operating line is as follows: ( )F W W L y x x x G , (2) where LF and G are the flow rates of liquid (reflux) and of vapor, mol/s; x is the concentration in liquid phase at the arbitrary section of the upper column, mol/mol (Fig. 1(a)). The corresponding equation for the lower column is: 0 0 0 F i L L y x x y G . (3) Fig. 1. Material flows (a) for the top and bottom sections of the column and operating lines (b) in у–x diagram built according to high- boiling component (arbitrary scale); L0, W and P are, correspondingly, flow rate of supplying isotope mixture, of waste (enriched with 20 Ne) and of target product ( 22 Ne). Table 1. Specifications of operating conditions on the top and bottom sections of the rectification column at the liquid feed by neon having ―natural‖ concentration of the high-boiling component (x0 = 0.0925) and outflowing streams xW = 0.015 and xp = 0.9999. E is description of the mode, degree of equilibrium in the stream delivery point; F is angular coefficient of lines in the 0Wx x area; TN , TN are NTP; 0iy is coordinate of the working lines crossing at 0x x ; F is angular coefficient of lines in the 0 Px x area. 0 0 0 0 D i D E y y E y y Top section Bottom section Total NT, pieces F F L G ,TN pieces 0iy 0F F L L G TN , pieces No-load. E = 0 1.0 (diagonal) 52.3 y0D = х0 = 0.0925 1.0 316 368 Intermediate conditions E = 0.2 0.992 59.8 y02 = 0.0919 1.00066 327 387 E = 0.4 0.984 70.6 y04 = 0.0913 1.00132 340 411 E = 0.6 0.977 88.3 y06 = 0.0907 1.00199 357 445 E = 0.8 0.969 125.6 y08 = 0.0901 1.00265 384 510 Minimal reflux E = 1 0.961 (equilibrium curve) ∞ y0E = 0.0895 1.00331 ∞ Cascade units for neon isotopes production by rectification method Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 619 Here L0 and x0 are flow rate and concentration of the vapor feed stream, mol/s; x is concentration in the liquid phase at the arbitrary section of the lower column, mol/mol; y0i is ordinate of the intersection of the top and bottom sections operating lines of the column (Fig. 1(b)). In the case when initial mixture is loaded to the column as a liquid, the ordinate of points y0i, where operating lines intersect, will be on the vertical line x0 = 0.0925 within the segment limits 0 0–  .D Eу у The calculation model consid- ers: ―no load‖ mode, corresponding to the absence of se- lection of the product P = 0 ( 0 0Dу x ); maximal loading in the case of minimal reflux ( 0Eу ), as well as four inter- mediate modes: у02, …, у08. The operating lines are spaced from the diagonal у = x by 20, 40, 60 and 80% of to the maximal distance, characteristic for the mode of minimum reflux ( 0Еу ). For the accepted concentrations of streams, the relative flow rate of the product Р/L0 varies with in- creasing of the loading from Е = 0 up to Е = 1.0 within the range of 0–0.0033. Therefore, the volume of the product having 99.99% isotopic concentration of 22 Ne does not exceeds one third of a percent from the flow rate of the supply substance L0. As our calculations show, the number of theoretical plates is calculated by hundreds. As the height of the trans- fer unit for the applied types of the packing makes dozens of millimeters (see Table 2), a column producing 22 Ne with isotopic quality of 99.99% and extraction coefficient С = 0.85 must have a considerable size. The height of the mass exchange part may reach 15–20 m. Such sizes lead to a considerable external heat leakage and complicate the cryogenic support of the unit. Factor of separation q of column and number of theore- tical plates NT in the case of no extraction of product (Р = 0) are specified by the Fenske formula [7]: 1 1 TNWP W P xx q x x , (4) where is separation coefficient of binary system ( = 1.037 for isotope pair 20 Ne– 22 Ne) [5]. 3. Separation of neon isotopes in cascade of rectification columns If the height of a single column is limited (see Table 2), it is impossible to obtain the high quality хР of ( 22 Ne) product. For this reason, the separation of isotopic compo- nents has to be made stage-by-stage. On some stages of separation the accumulation of 21 Ne isotope contained in the initial mixture in 0.28% concentration is performed. Figure 2 outlines schemes of successive concentration of the high-boiling 22 Ne and intermediate 21 Ne + 22 Ne isotopic components. Naturally, xW mixtures enriched with low-boiling 20 Ne are removed from the waste mixture cir- cuits. The first scheme (Fig. 2(a)) provides multiple process- ing of intermediate fractions in the same column [6]. Ob- viously, the performance of such method is low and to in- crease it the cascade connection of several columns is applied (Fig. 2(b)). The feature of the second scheme is the return of waste fractions xW2 and xW3 to the previous sec- tions (1 and 2) for reprocessing. For this purpose at each next step the pressure relative to the previous one is in- creased: P1 < P2 < P3. Both in the first and the second case (Figs. 2(a), (b)) the feed of bottom product xPi to the col- umn for re-separation processes is accompanied by a num- ber of unproductive processes. The resulting intermediate fractions xPi must be forced- ly heated up to ambient temperature, collected in a gas tanks, compressed, cleaned of impurities, cooled, and then let in another column (option (b)) or in the same column (option (a)). Unfortunately, these procedures result in losses of expensive isotopic components, enriched by the target products ( 21 Ne + 22 Ne). More perspective, in our opinion, is third option (Fig. 2(c)), where the valuable products are supplied di- rectly to the subsequent stages of cascade (xP1 — to the column 2, xP2 — to the column 3, etc.) in cold state. Thus, less valuable products, enriched by predominant compo- nent 20 Ne are supplied to the block 9 for collection, storage and purification of fraction. The scheme presented in Fig. 2(с) can function without returning of waste streams. Table 2. Comparative characteristics of the packed rectification columns, used by authors for neon separation into isotopes (in the no-load mode: Е = 0). xW and xP are concentrations of the high-boiling component 22 Ne; SP is spiral-prismatic packing; SC is spiral- cylindrical packing. Diameter, mm xW xР NTP, NT, pieces (4) Height of the theo- retical plate, mm q is separation factor (4) Specific surface area of packed bed, m 2 /m 3 22 0.003 0.985 275 28.7 21 800 5300–SP 25 0.004 0.983 263 30.0 14 400 5200–SP 25 0.02 0.98 215 30.5 2 400 5000–SP 32 0.06 0.92 150 42.0 180 4000–SC 35 0.05 0.95 160 40.1 360 3500–SC 50 0.01 0.5 130 50.4 100 3500–SP 50 0.015 0.4 105 61.0 45 1900–SC V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko and E.V. Matveyev 620 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 In this case xWi fractions are collected and used, e.g., for preparation of mixtures with modified (different from natu- ral) isotopic ratio. For the operation of the circuit shown in Fig. 2(с), the driving difference of pressure between the stages P1 > P2 > P3 must be maintained. Such driving pressure difference can be achieved through the different thermal loading in vaporizers of bottom section of the column 3 (Fig. 3(a)). An important operating advantage of the scheme, shown on Figs. 2(b) and 3(a), is the decreased pressure in the end column III. Thus the coefficient of relative volatili- ty (separation factor) of the isotope pair 20 Ne + 22 Ne is increased with reduction of the working pressure [5]. In Figs. 2 and 3 all stages are conventionally shown as columns of the same diameter. Meantime most cascade units use circuits with step-by-step decreasing performance of elements [8]. Decrease of the flow rate х01 > x02 > x03…. allows reducing the time required to achieve the stationary state in the columns of cascade. For illustration of this phenomenon we will introduce the special factor — rela- tive performance of rectification devices: 0 0 1 2 3( ) L L V k v v v h –1 . (5) Here L0 is the flow rate of the product processed, norm. dm 3 /h; v1 + v2 + v3 is the total hydraulic volume of the column, dm 3 , that consists of volumes of packing sec- tion (1), of condenser (2) and of bottom section of the column (3), correspondingly (see Figs. 2 and 3); = = 0.16–0.18 is the filling fraction of volumes 1, 2, 3 by liquid neon; k = G / L= 1450 is volume of neon, norm. dm 3 , pro- duced at evaporation of 1 dm 3 of liquid ( G = 0.829 g/dm 3 is density of gaseous neon at Р = 0.1 МPa and Т = 293 K; L = 1206 g/dm 3 is density of liquid neon). As it follows from data provided in Ref. 6 and results of our tests, the size for the primary column of cascade in the mode of 22 Ne production is 22 = 0.10–0.12. When the target product is 21 Ne, the relative flow rate is decreased up to 21 = 0.014–0.018. Being a nominal index, factor , at the same time, shows what amount of time necessary for initial accumulation of target products in columns. If this factor is not taken into account and there is no replacement of isotope products in reflux, which fills the cavities of devices, it is possible to produce only partly enriched products. Production of concentrated substances is possible only as a result of accumulation of sufficient volume of target product in columns (especially end sec- tions). Minimum time (hours), required for stabilizing of concentrations, to a first approximation is 01 mх х h, (6) where 01 3 0.5( )m Рх x х is the average concentration of the target product in the columns of the cascade, mol/mol. Fig. 2. Options of the multistage separation of isotopic compounds: on the basis of the same rectification column (a); cascade connec- tion of columns with heating of intermediate fractions, enriched by target products (b); cascade connection of columns with heating of intermediate fractions, depleted by target products (c). 1 is rectification columns; (I)–(III) is number of the stage; 2 is condenser; 3 is vaporizer of the bottom section of the column; 4 is heat exchanger; 5 is gasholder; 6 is compressor; 7 is receiver; 8 is adsorber; 9 is collection, storage and fractions purification block. Cascade units for neon isotopes production by rectification method Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 621 Taking into account empiric values of 22 and contents of 22 Ne in the initial neon stream having natural composi- tion (x0 = 0.0925), one gets 22 100 h. Analogically, for 21 Ne (x0 = 0.0028) production the necessary time is 21 > 20 000 h! To reduce this period the deep concentra- tion (saturation of reflux by target product) is applied usually only at the end columns of the cascade. The same result can be achieved by reduction of volume (diameter) of columns of end cascades and by increase of the initial section size. According to Eqs. (4) and (5), the initial sec- tion determines the quality of the target product, supplied to the separation circuit. In other words, only the high per- formance at initial stage can provide the operation of low- capacity output column. Meantime, practical implementation of this technical solution doesn’t give the expected result. An attempt to increase the flow rate in the initial column by increasing diameter of its section results in the sharp drop of the sepa- ration factor q (Table 2). The degree of extraction of target products (1) accumulating in the packing as a reflux, is decreased. This negative phenomenon can be leveled by using several small-scale columns forming initial stages of cascade (Fig. 4(a)). Theoretically, all columns of the cas- cade must be unified, and their number at all stages must be gradually decreased [9]. Such reduction will lead to redistribution of streams between sections. This will, in turn, affect the inclination of the operating lines expressed by Eq. (3) (Fig. 4(b)). Fig. 3. Cryogenic cascade setup maintenance identical to Fig. 2(с). 1–4 are the same as in Fig. 2; 5 is compressor of the neon throttle cycle cooled by liquid nitrogen. Fig. 4. Cascade setup (Figs. 2(с) and 3(a)), formed from the same type columns (a) and character of operating lines (b) in у–x diagram built according to high-boiling component (arbitrary scale). V.L. Bondarenko, Yu.M. Simonenko, O.V. Diachenko and E.V. Matveyev 622 Low Temperature Physics/Fizika Nizkikh Temperatur, 2013, v. 39, No. 5 The research carried out allows creating the series of industrial units for production of neon isotopes with con- centration up to 99.99%. 4. Conclusions Ukraine is traditionally a leading exporter of rare gases. Our country produces about a half of the world amount of high purity neon. Future progress in isotope technologies is an actual and logical part of the integrated technological sequence of the light inert gases production from atmos- pheric air. Rectification is an effective method of separation of gases with relatively small molecular weight. However due to almost identical physical properties of isotope compo- nents the separation coefficient doesn't exceed 1.040. It results in a large number of theoretical plates and in consi- derable column height (> 15 m). Cascade scheme of the rectification devices assembly makes it possible to reduce several times vertical dimensions of the unit, as well as heat leakage and maintenance costs of cryogenic process. According to the technical solutions presented in this article, a series of cascade units for Ne separation into iso- topes was created. Under conditions of the limited availa- ble height of rectification columns the record results on 21 Ne enrichment are obtained, as well as 20 Ne и 22 Ne with isotope concentration more than 99.99% were produced. 1. A.I. Brodsky, Stable Isotopes of Light Elements, Success of Physical Sciences, Edition 2 (1988), Vol. XX, p. 153. 2. V.V. Azarova, Yu.D. Golyaev, G. Dmitriev, M.S. Drozdov, A.A. Kazakov, A.V. Melnikov, M.M. Nazarenko, V.V. Svirin, T.I. Soloviova, and T.V. Tikhmenev, in: Optical Gyros and their Application, NATO, RTO AGARDograph 339, 5 (1999). 3. А.М. Arkharov, I.A. Arkharov, V.L. Bondarenko, Yu.M. Si- monenko, M.Yu. Savinov, and А.S. Bronshtein, Nontradi- tional Technologies of Obtaining the Concentrates of the Isotope of 20Ne, Proc. 8th Intern. Conf. ―Cryogenics–2004‖, Prague (2004), p. 175. 4. M. Benedikt and T. Pigford, Chemical Technology of Nuclear Materials, Atomizdat, Moscow (1960). 5. B.M. Andreev, Ya.D. Zelvensky, and S.G. Katalnikov, Separation of Stable Isotopes by Physics-Chemical Methods, Energoatomizdat, Moscow (1982). 6. L. Bewilogua, P. Verges, and H. Vinzelberg, (1977), Isoto- penpraxis, Bd.9: 97. 7. M. Fenske, Industrial & Engineer. Chem. 24, 482 (1932). 8. А.М. Rozen, Theory of Isotope Separation in Columns, Atom- izdat, Moscow (1960). 9. V.L. Bondarenko and Yu.M. Simonenko, Unit for Separation of Gas Mixtures in Rectification Columns. Patent № 121753 RF for utility model. Priority 20.03.2012. Application #2012110459. Registered in Public register 10.11.2012.