THE CECE EXPERIMENTAL INDUSTRIAL PLANT FOR REPROCESSING OF TRITIATED WATER WASTES

I.A. Alekseev, S.D. Bondarenko, O.A. Fedorchenko, A.I. Grushko, S.P. Karpov, K.A. Konoplev, V.D. Trenin, E.A. Arkhipov, T.V. Vasyanina, T.V. Voronina Petersburg Nuclear Physics Institute 188300, Gatchina, Leningrad district, Russia +7-81571-31985

V.V. Uborsky JSC DOL Moscow, Russia +7-095-4967928

ABSTRACT The experimental industrial plant for hydrogen isotope separation on the basis of the methods of chemical isotope exchange between water and hydrogen and water electrolysis (CECE process) is under operation in Petersburg Nuclear Physics Institute. The large-scale studies of hydrogen isotope separation have been ongoing at this plant since 1995. The plant is also used for reprocessing tritium heavy water waste; several tons of reactor quality heavy water have been obtained. The EVIO-4 code allows one to predict the concentration profile in the column under parameter changes. The calculation results are in compliance with the experimental data. The 18,000 hours experience gained during the plant operation shows the high efficiency of isotope separation by CECE process and allows us to regard this process with considerable promise for the industrial use, in particular, for water purification from tritium. I. INTRODUCTION Nuclear reactors moderated by heavy water require upgrading facility to maintain deuterium concentration in water and facility for tritium recovery. Future fusion reactors also require Isotope Separation System for tritium extracting mainly from light water. The CECE process offers a more flexible and cheaper alternative for upgrading and detritiation than conventional DW-VPCE in both nuclear and fusion reactor applications1. The experimental industrial plant2 for hydrogen isotope separation on the base of the CECE process has been built in Petersburg Nuclear Physics Institute in cooperation with JSC "DOL" and D. Mendeleev University of Chemical Technology of Russia. The main purpose of the plant is the development of the technology of tritium and protium removal from heavy water of PIK hi-flux reactor. This paper describes the facility and presents experimental data on its separation performance for both deuterium and tritium. The experimental data are compared with the ones predicted by computer simulation.

II. BRIEF DESCRIPTION OF THE PLANT The schematic flow diagram of the plant is presented in Figure 1. The chemical exchange column of 7.5 m overall height and an inner diameter of 100 mm is filled with alternating layers of wetproofed catalyst and stainless steel spiral-prismatic packing. The column consists of three separation sections connected through a distributor of liquid. Each section is provided with a heating water jacket for maintaining the column temperature within 300-360 K.

Figure 1 - Schematic flow diagram of the plant The operating pressure is 0.13 - 0.4 MPa. The sections of the column are bolted together. This enables an easy replacement of catalyst and packing if it is needed. The feed points (FP) and sample points (SP) are located between the separation sections, at the top and at the bottom of the column. The overall separation height of the

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column is 5.9 m. Used wetproofed catalyst has been developed by D. Mendeleev University of Chemical Technology of Russia. It consists of 0.8 % wt. platinum deposited on porous polysorb (styrene-divinylbenzene copolymer)3. The plant uses alkaline electrolysis cells as a lower reflux device and hydrogen catalytic burners as an upper reflux device. The hydrogen output of electrolysis cells is 5 m3/h. All equipment of the plant was manufactured in Russia. The plant operation is semiautomatic. Personnel are required to carry out various adjustments and analyses. Two persons ensure operation4. A computer monitoring and control system automatically maintains water flows supplying into the column and provides an on-line product analysis for deuterium contents. III. EXPERIMENTAL TECHNIQUE Separation performance of the column was determined by measuring the deuterium and tritium concentration in water and gas from different sample points (see Figure 1: SP0 and SP4 are for gas and the all others for water). The results were obtained at the quasi steady-state mode of operation of the plant. At this mode the isotope concentrations across the column practically were not changing in course of time but the concentrations in water stream leav-

ing the column and in the hydrogen gas entering the column were not always equal to each other. Deuterium (protium) contents in water samples were analysed by the IR-spectrophotometer with a relative accuracy to 1%, in gas samples - by gas chromatography to an accuracy of 4%. Tritium was measured by the liquid scintillation method accurate to 10%. The computer control system of the plant provides automatic maintenance of the liquid stream flow rates with accuracy not worse than 1%. IV. OPERATING MODES The plant is operated in different modes. The examples of the three modes operation characteristic are presented in Table 1. And the achieved results are shown in Table 2. It is necessary to pay attention to the fact that the selected experiments differ not only in conditions under which they were conducted; these experiments present modes differing by their goals. The first mode is the main mode of processing dilute heavy water waste contaminated by tritium. The most time of the operation the plant works in this mode. Only one difference can appear upper reflux device can be switched on or off. In the case presented in the table the

Table 1 - Three Modes Selected Experiments Initial Parameters Parameter Mode 1 Mode 2 Pressure, kPa 169 251 Pressure drop, kPa 7.2 2.6 67 84 Temperature, C 12 14.6 Condenser temperature, C Isotope D, at. % T, Ci/l D, at. % T, Ci/l Reflux Flow rate, ml/h 2002 1690 Stream Isotope composition 0.015 2.9e-7 99.810 3.0e-6 Feed Flow rate, ml/h 2901 0 Stream Isotope composition 47.90 2.1e-3 Hydrogen load, m3/h (STP) 4.390 2.320 Hydrogen stream composition a 99.931 3.3e-3 99.999 2.1e-3 Electrolysis feed flow rate, ml/h 3528 1864 Sample Point Isotope SP4 (gas) SP4 (water after condenser) SP3 SP2 SP1 Product output, kg/month
a

Mode 3 199 5.85 75 12.1 D, at. % T, Ci/l 3005 0.015 2.0e-7 0 3.723 99.988 4.2e-3 2982 Mode 3 D, at. % 0.27 0.024 77.4 99.984 99.996 --

Table 2 The Results of the Experiments Mode 1 Mode 2 D, at. % T, Ci/l D, at. % T, Ci/l 1.28 99.828 0.027 2.9e-7 99.809 3.2e-6 45.4 1.7e-3 99.987 1.35e-5 86.8 2.0e-3 99.999 1.3e-4 99.931 3.6e-3 99.999 2.3e-3 1075 (bottom product) 135 (top product)

T, Ci/l 1.8e-7 1.9e-5 2.5e-4 4.2e-3

Tritium contents in the gas is presented in Curie per litre of water forming after combustion

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catalytic recombiner was switched off, the hydrogen stream exiting the column was vented to the atmosphere through a stack, and distilled water was fed to the top of the column like a reflux stream. As is seen from the table 1.075 ton per month reactor grade heavy water is obtained as a result of dilute heavy water processing. The second mode is the example of tritium removing from heavy water that is decomposed in the Electrolysis Cells. Heavy water with reduced contents of tritium (de3 contamination factor is about of 10 ) was withdrawn at the rate of 4.5 kg per day as a top product in Mode 2. The third mode was only experimental with the goal to see the capabilities of our column in heavy water detritiation under the conditions different from those of Mode 2. The column worked according to the scheme with independent streams, upper reflux device was switched off. In such a mode the column was operated relatively for a short time. V. THE EXPERIMENTAL DATA IN COMPARISON WITH ONES PREDICTED BY THE COMPUTER MODEL The experimental data (diamonds) in comparison with the computer simulation curves are presented in Figures 2-4. On the left side one can see the tritium profile across the column and on the right deuterium profile. A scrubbing layer number is laid off on abscissa axis. Zero number corresponds to the bottom of the column. The axis of ordinates is atomic fraction of tritium or deuterium. Figure 3 - Tritium and Deuterium Profiles in Mode 2 The curve in the left chart is calculated tritium contents in liquid. In the right chart According to deuterium experimental points in Mode there are two calculated curves: for deuterium contents in 3 (Figure 4) the middle section has the highest separation liquid (upper) and in gas. The coincidence of computer performance due to very high deuterium concentration model with the experiment for both isotopes is clearly seen obtained at scrubbing layer 188 (see SP2). That is why in Figure 2 (Mode 1). there is the slope change of tritium profile at this point. The same situation is for Mode 2 (see Figure 3). Looking at the slope of the lines in tritium profile corresponding to different sections of the column one can see that the lower section has higher separation performance than the middle one. And the middle section in its turn works better than the upper one. The fact is interesting taking into consideration that the packing of the separation section was almost identical. The deuterium profile looks flat here because of low scale resolution. The model gives more optimistic separation forecast in case when expected tritium contents across the considerable part of the column were much lower (up to 2 orders of magnitude) than it was in Mode 1. Very likely that changing Mode 1 by Mode 3 we could come to the situation when the inner packing of the column could act as tritium sources. Of course, they were not taken into account by the code.

Figure 2 - Tritium and Deuterium Profiles in Mode 1

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VI. COMPUTER SIMULATION OF THE FACILITY Simulation code EVIO-4 deals with three streams (liquid water, water vapour and hydrogen gas). The mathematical model5 of the process has been improved. The Murphreetype factors are introduced in the code to consider the efficiency of both scrubbing and catalyst layers. Two constants, which define each of the factors for catalyst and scrubbing layers, are reverse reaction rate constants of hydrogen/vapour catalytic exchange and water/vapour phase exchange. The code provides stable and rapid computation of a concentration profile if values of both constants for each separation section are known. However, we cannot so far solve completely the inverse problem that is, unique determination of these constants if the concentration profile is experimentally known. The experimental profile of an isotope concentration measured only in a liquid phase can be well described by the computer model in both cases: when high values of constants for catalytic exchange and low values for phase exchange are given and vice versa. In fact this is the problem of two low sections, the reason of which is vapour sampling points absence between the sections of the column. The situation is quite different for the upper section due to Sampling Point 4 (water after condenser). Nevertheless EVIO-4 makes it possible a correct forecast of deuterium concentration profile within the column operated under conditions (temperature, pressure and values of water and gas flow rates) different from those under which the constants are measured. In Figure 5 the initial data and Mode 1 calculation results (table in the lower part) are Figure 5 The Interface of the Simulation Code EVIO-4 presented. A lot of items in the interface are understandable due to the given column service functions making the work with the model easier. scheme and the fact that the values of some initial data For example it is enough to press the small button to see coincide with ones given in Table 1. Here are some others: the graphic representation of the results as it shown in FigD=0.1m inner diameter; hscr=0.008 m a scrubbing ure 6. There are some capabilities, which allow us to draw layer height; hcat=0.002 m a catalyst layer height; not only the profiles of different isotope concentrations in N=573 the total number of catalytic layers; NF=368 various flows (liquid, gas and vapour) but more others as feed scrubbing layer number; jT2=188 and jT3=368 the well. For example, one can see how separation factors as upper scrubbing layer numbers of the lower and the middle well as both catalytic (Kg) and phase exchange (Kl) mass sections accordingly; G=369 Amperes current through transfer rates are changing across the column. Experimenthe electrolysis cells; kL1 and kV1 two constants, which tal points (Figure 6) can be input in order to see in the define efficiencies of scrubbing and catalyst layers for the chart how the model describes the experiment. first separation section; et cetera. There are a number of

Figure 4 - Tritium and Deuterium Profiles in Mode 3

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The deuterium transfer rates for the upper section of the column were uniquely evaluated by the code as the following average values for Mode 1: Kg3=46.5 mol*m-3*s-1, Kl3=113 mol*m-3*s-1.

Supposing the phase exchange for the lower sections the same as for the upper one we received the following average values of the catalytic transfer rate: Kg1=150 mol*m-3*s-1, Kg2=76.5 mol*m-3*s-1. These values are given here only for comparison between separation performances of the sections. We understand quite well that the phase exchange may be more responsible for such difference than the catalytic exchange, especially for Mode 1. By now, unfortunately, there is no possibility to find unique relation between catalytic and phase exchange transfer rates for lower sections. VII. FUTURE PLANS The plant has been working continuously since 1998. Processing heavy water waste, it produces heavy water and deuterium gas of 99.85 99.999 at. %. In spite of the existence of the wide enough industrial programme - 2-3 runs per year with duration of 2-5 months, improvements are being made to the plant. For example the height of the column was increased recently to obtain higher separation performance for heavy water detritiation. And besides this we are going to construct another column especially for heavy water high purification from tritium. Two approaches are given into consideration a new type exchange reaction column6 and traditional one. 3. We consider the vapour phase sampling between the sections of the column is of great importance because it will help to delimit uniquely the influence of each abovementioned process (catalytic and phase exchange) on separation performance of the column in different modes. And we plan to solve successfully this problem in the near future. VII. CONCLUSIONS 5. Figure 6 EVIO-4: Results Graphic Illustration REFERECES 1. D.A. Spagnolo and A.I. Miller, The CECE Alternative for Upgrading/Detritiation in Heavy Water Nuclear Reactors and for Tritium Recovery in Fusion Reactors, Fusion Technol., 28, 748 (1995). I.A. Alekseev, S.D. Bondarenko, T.V. Vasyanina et al., The Study of CECE Process at the Experimental Industrial Plant, Proc. of the 20th Symposium on Fusion Technology, Marseilles, France, 7 11 September 1998, p. 959, EUROATOM-CEA (1998). B.M. Andreev, Y.A. Sakharovsky et al., Installation for Separation of Hydrogen Isotopes by the Method of Chemical Isotopic Exchange in the "Water-Hydrogen" System, Fusion Technol., 28, 515 (1995). I.A. Alekseev, S.D. Bondarenko, O.A. Fedorchenko et al., Operating Experience of the Experimental Industrial Plant for Reprocessing of Tritiated Water Wastes, Fusion Engineering and Design, 58-59, 439 (2001). O.A. Fedorchenko, I.A. Alekseev, V.D. Trenin, V.V. Uborsky, Computer Simulation of the Water and Hydrogen Distillation and CECE Process and Its Experimental Verification, Fusion Technol., 28, 1485 (1995). O.A. Fedorchenko, I.A. Alekseev, V.D. Trenin, A New Type Separation Column for the WaterHydrogen Isotope Catalytic Exchange Process, Fusion Engineering and Design, 58-59, 433 (2001).

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The experience gained during the plant operation shows the high efficiency of hydrogen isotope separation. We consider that CECE process has immediate potential to upgrade of downgraded reactor heavy water and to separate tritium from light or heavy water. CECE process will be used in the plant for tritium and protium removal from heavy water of PIK reactor. Optimal operation parameters of the future facility are being studied now by the computer simulation code EVIO-4.

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