WO1981000413A1 - Methode pour le traitement de courants gazeux emis pendant un procede nucleaire - Google Patents

Methode pour le traitement de courants gazeux emis pendant un procede nucleaire Download PDF

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Publication number
WO1981000413A1
WO1981000413A1 PCT/US1980/000992 US8000992W WO8100413A1 WO 1981000413 A1 WO1981000413 A1 WO 1981000413A1 US 8000992 W US8000992 W US 8000992W WO 8100413 A1 WO8100413 A1 WO 8100413A1
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Prior art keywords
krypton
adsorbent bed
gas stream
set forth
gas
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PCT/US1980/000992
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English (en)
Inventor
D Pence
C Chou
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Science Applic Inc
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Publication date
Priority to AU62299/80A priority Critical patent/AU6229980A/en
Application filed by Science Applic Inc filed Critical Science Applic Inc
Priority to DE19803049761 priority patent/DE3049761A1/de
Publication of WO1981000413A1 publication Critical patent/WO1981000413A1/fr

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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/02—Treating gases

Definitions

  • the present invention relates to nuclear process off-gas treatment systems, and more particularly to a method for selectively removing and recovering for long- term storage, if necessary, the noble gas and other gaseous components typically emitted during nuclear process operations.
  • the described method is adaptable and useful, for example, in treating the dissolver off-gas effluents released during reprocessing of spent nuclear fuels whereby to permit radioactive contaminant recovery prior to releasing the remaining off-gases to the atmosphere.
  • Activation and fission products are released and become airborne during nuclear fuel reprocessing of light water reactor fuels. Certain of these products are long-lived and, accordingly, represent a serious hazard to people if the products are released directly into the local environment.
  • the products of primary concern are tritium, carbon-14, krypton-85, iodine-129, and some of the fission product semivolatile metal oxides such as ruthenium, technetium, and antimony.
  • Iodine-131 may also be present in hazardous amounts if the spent nuclear fuel is reprocessed within about 180 days following reactor discharge. In most instances the radioxenons will have decayed prior to fuel reprocessing.
  • Some methods propose a preliminary heat-treatment step following shearing of the spent fuel bundles whereby to release a large fraction of the volatile activation and fission product gases. Most of the remaining volatile gases are subsequently released during the fuel dissolution step.
  • three off-gas streams containing activation and fission product gases are released: (1) an off-gas stream from the heat-treatment step; (2) an off-gas stream released from the dissolver; and (3) an off-gas stream from the various vessels comprising the remainder of the fuel reprocessing system.
  • a heat treatment step is included in the design of an off-gas treatment system, essentially all of the tritium and appreciable quantities of the iodine and noble gases will be released to the heat-treatment step off-gas stream. Due to the high concentration of tritium in this off-gas stream, the most practical approach is to remove the tritium, and possibly the iodine, and then return the noble gases and any carbon- containing gases that may be present to the off-gas stream released from the dissolver. If a heat-treatment step is not included in the method, the tritium will be released during dissolution of the fuel and most of the tritium will exchange with the nitric acid dissolver solution. Noble gases present in the dissolver will be quantitatively released to the dissolver off-gas stream. Most of the carbon-14 containing compounds, the majority of which are in the form of carbon dioxide, and greater than 95% of the iodine will also be released to the dissolver off-gas stream.
  • cryogenic distillation method differs primarily in their approach to removing contaminant gases, other than xenon and krypton, in a nitrogen carrier gas stream. These processes have been described at several recent conferences and in publications promulgated to the various participants. IAEA, Proceedings of International Symposium on the Management of Radioactive Wastes from the Nuclear Fuel Recycle, Vienna, Austria, 22-26 March 1976; and M. W. First, Ed. , Proceedings of the 15th DOE Nuclear Air Cleaning Conference, 7-10 August 1978, Boston, Mass., CONF 780819, February 1979. To prevent the freeze-out and plugging of contaminant gases in a cryogenic distillation unit, an efficient pre-treatment contaminant gas-clean-up must be used.
  • contaminant gases such as C0 2 , NO x (including N 2 O, NO, NO 2 , and N 2 0 4 ), and various hydrocarbons, must be removed to about 1 ppm. to ensure trouble-free operation.
  • a radiolysis product of oxygen in high radiation fields caused by concentrated krypton- 85 the oxygen concentration in the off-gas stream should be kept low. J. F. Riley, "Radiolysis of Liquid Oxygen and Oxygen-Nitrogen at 77° K," Chemistry Division Annual Progress Report for Period Ending June 20, 1963, ORNL-3488.
  • cryogenic selective adsorption- desorption has been proposed for the removal of noble gases.
  • T. Kanazawa, et al. "Development of the Cryogenic Selective Adsorption-Desorption Process on Removal of Radioactive Noble Gases," Proceedings of the 14th ERDA Air Cleaning Conference, 2-4 August, 1976, Sun Valley, Idaho, CONF-760822, February 1977.
  • noble gases in particular xenon and krypton
  • present in a nuclear process off-gas stream may be selectively removed in gas phase.
  • This generic form of the invention is adaptable and useful in an integrated process for effecting the treatment of off-gas effluents released during nuclear fuel reprocessing.
  • the integrated process comprises: (a) passing the dissolver off-gas stream through a NO adsorption column wherein NO 2 is caused to react with water to produce NO and nitric acid; (b) destruction of the NO and remaining
  • the present invention possesses several advantages, among which is that the production of liquid wastes is significantly reduced. Yet another advantage is that the majority of process steps are carried out at about ambient temperature and pressure. Still further, the sequence of steps to be performed in practicing the process has been selected to ensure the compatibility of each step with all subsequent process steps. In this manner the overall efficiency of the process to treat a nuclear process off-gas stream is significantly increased.
  • Figure 1 is a diagrammatic view of the process adapted for treating a dissolver unit off-gas stream.
  • Figure 1 diagrammatically illustrates an integrated process for removing and recovering airborne activation and fission product radioisotopes released to a dissolver unit off-gas effluent stream during nuclear fuels reprocessing. While the process hereafter disclosed here is primarily directed to dissolver off-gas effluents treatment, persons skilled in the art will readily comprehend that slight modification can be made thereto rendering the process campatible for treating, in addition, both heat- treatment and vessel off-gas effluent streams.
  • the oxides of nitrogen included within the dissolver off-gas effluents stream first be removed. Therefore, the various off-gases released from the depicted dissolver unit 10 are initially directed through an NO adsorption column 11 and condenser 12 wherein a major portion of NO 2 is converted to NO and and nitric acid by reaction with water, these reaction products being recycled through line 13 back to dissolver unit 10. The remaining off-gas effluents, including residual NO 2 and major amounts of NO, are then directed through an interchanger 14 and heater 15 prior to entering an NO x destructor 16.
  • the NO components entering destructor 16 are catalytically reduced to nitrogen and water.
  • the manner by which said components are catalytically reduced is more fully disclosed in pending U.S. Serial No. 504, 793, filed September 10, 1974, an application in which Dallas T. Pence, a co-inventor of the present invention, is a joint applicant. That application is a continuation-in-part of U.S. Serial No. 284,810, filed August 30, 1972. Briefly, reduction occurs by passing the off-gases over a bed of hydrogen-formed synthetic mordenite, maintained at about 400° C, and using ammonia as a reducing gas.
  • the remaining off-gas effluents are redirected through interchanger 14 wherein they are cooled to about 150° C, interchanger 14 simultaneously heating the feed gas to NO x destructor 16 by heat transfer.
  • the cooled off-gases exiting interchanger 14 next enter an iodine adsorbent bed 17 wherein the radioiodines, including iodine-129 and trace quantities of iodine-131, are removed.
  • Adsorbent beds 17 may beneficially comprise either silver-exchanged zeolite, either in the ionic reduced form, or silver-impregnated amorphous silicic acid catalyst material. Because the most suitable operating temperature for using these materials is about 100° to 150° C, the off-gases from destructor 16 are first cooled in interchanger 14 prior to passing through an iodine adsorbent bed 17.
  • iodine adsorbent beds 17 are used in parallel, one of said beds being on line to receive off-gas from interchanger 14 while the other of said beds is either being replaced when spent, in standby condition, or in the process of being regenerated by a method such as that taught in T. R. Thomas, et al., Airborne Elemental Iodine Capacities of Metal Zeolites and a Method for Recycling Silver Zeolite, ICP-1119,
  • the removed water may be either stored or alternatively recycled back to the dissolver unit 10.
  • the average composition of the off-gases exiting condenser 18 is approximately as follows: 56,000 ppm. (assuming the cooler condenser temperature is approximately 35° C) ; 2,500 ppm. xenon; 300 ppm. CO 2 ; 250 ppm. krypton; 20% O 2 ; 1% argon; and the balance nitrogen. These concentrations are given as averages; however, the concentrations will vary considerably depending upon the type of dissolver, continuous or batch, and the time for the dissolution cycle.
  • the off-gas effluents exiting condenser 18 are next directed through line 34 to water vapor removal means 30 , said means comprising at least two water removal columns 31, or the like, disposed therethrough with an adsorbent preferentially adsorptive towards water vapor. Separation of water is obtained using conventional adsorption-desorption technology at essentially ambient temperature and pressure. What is meant by conventional adsorption-desorption technology is that the contaminant-containing gas is passed through a column, or the like, containing the selective adsorbent material and one of the contaminants is selectively adsorbed while the remaining gases readily pass therethrough.
  • the feed-gas stream is shifted to a standby column, and the loaded column is then heated and the collected contaminant gas purged from the heated adsorbent bed with air.
  • the recovered contaminant gas is then in a highly concentrated form which can either be recovered or fixed for long-term or permanent disposal.
  • relatively uniform flow of the effluents exiting condenser 18 is obtained by interposing a blower 20 to compress the effluents to several psi. within surge tank 21.
  • a flow regulator (not shown) is used to ensure a uniform discharge from surge tank 21.
  • blower 20 and surge tank 21 may be interposed at different positions within the process scheme, such as upstream of the NO x destructor 16, depending upon the preferred operation of the NO X destructor 16 and iodine adsorbent beds 17. While the uniform flow rate of the effluents from condenser 18 is not critical, the determination of the most efficient operation for the subsequent stages in the process is easier to calculate with uniform feed rates.
  • the feed rate to a water removal column 31 should be such that the actual face velocity of the gases through column 31 is about 9.15 m./min. when the adsorbent material is in the particle diameter size range of about 10-20 mesh (U.S. Standard).
  • the adsorbent material used for selective water removal is a Type 3A Zeolite molecular sieve which will also coadsorb approximately 10% of the CO 2 present, but does not co-adsorb any of the other gaseous constituents to any appreciable extent (less than 1 ppm.).
  • the dissolver off-gas flow rate will vary considerably depending upon the size and design of the reprocessing facility, but for a facility with a dissolver off-gas 3 rate of about 3.0 m. /min. , the diameter of the water removal columns 31 would be approximately 0.61 meters.
  • average concentrations of H 2 O in the effluent from a water removal column 31 will be less than 1.0 ppm.
  • the feed stream through line 34 is transferred to a standby column 31, and a purge flow of air from blower 40 and through line 36 is introduced into the saturated column 31 at approximately the same face velocity as for the feed gas and for a period of time of about 5 to 10 minutes.
  • the forward purge and discharge lines, 36 and 37, respectively, are then closed and electrically heated column clamp heaters 32, or the like, turned on.
  • the water removal column undergoing regeneration is vented through vent line 39. As the column 31 is heated to the desorption temperature of about 275° C, water vapor is released.
  • the back-purged air supply line 38 is open and air from blower 40 is heated within heater 41 and passed through column 31 at a rate of approximately l/15th that of the forward feed rate.
  • the exact purge rates and times depend, of course, upon the specific design.
  • vent line 39 is closed, and the column 31 and adsorbent disposed therein cooled to ambient temperature by external water-cooled coils 33, or the like, wrapped and welded around columns 31 between clamp heaters 32. If the columns 31 are large, dry air through the back-purge line 38 may be introduced to cool the bed quickly enough to be ready for the next loading cycle.
  • the tritium-contaminated recovered water can either be recycled to dissolver 10 or solidified for long-term waste storage. Any CO 2 that was co-adsorbed with H 2 O should be recycled back to dissolver 10.
  • the forward-purge gas and any residual off-gas effluents removed from columns 31 by the forward-purge cycle are directed by line 37 for recycle to dissolver 10 by way of line 42.
  • the outlet gas exiting water removal means 30 is next directed through line 35 to CO 2 removal means 50.
  • Means 50 comprises at least two CO 2 removal columns 51 , or the like, having column dimensions, operating conditions, and operating procedures substantially identical to those of water removal columns 31.
  • the loading through line 35, forward-purgeing through line 56, venting through line 59, and back-purging through line 58 operations are the same.
  • pressure surges due to forward-purge flow may be accommodated in the system by directing said flow via line 57 back to dissolver unit 10.
  • the only difference in these operations is that the loading times for column 51 are slightly longer for the same column dimension, and the required desorption temperatures are slightly reduced, to about 250° C.
  • a Type 4A zeolite molecular sieve is used as the adsorbent in columns 51 for the selective adsorption of CO 2 . It has been demonstrated that carbon dioxide will not break through a 0.915 meter long column for approximately 12 hours. The average concentrations of co-adsorbed xenon and krypton are less than 0.1 ppm. in the back-purged CO 2 effluent.
  • Heating and cooling of the columns 52 is performed by means of external clamp heaters 52 and water-cooled coils 53.
  • the CO 2 recovered through vent line 59 can be further concentrated in yet another adsorption step, solidified directly into a matrix compressed for steeltank storage, or directly released to the atmosphere. However, because this gas stream will be enriched in carbon-14, a waste recovery procedure for the recovered CO 2 is preferred.
  • Means 70 comprises at least two xenon removal columns 71, or the like, having dimensions, operating conditions, and operating procedures substantially identical to those used for the water removal columns 31 and CO 2 removal columns 51. The essential differences are the type of adsorbent utilized, the desorption temperature, and the desorption procedure.
  • the adsorbent used for xenon separation is silver- exchanged synthetic mordenite.
  • This material was prepared from a base material purchased from the Chemical Process Products Division, Norton Company, Akron, Ohio, and described in Bulletin Z50 of that company as Zeolon 900, hydrogen form.
  • the Zeolon 900 material is a zeolite material composed of sodium silicates.
  • the hydrogen form is that in which the sodium cations have been replace with hydrogen ions.
  • the Zeolon material was received as 1/8 in. diameter by 1/4 to 3/8 in. long extrudate pellets. The material was ground and sieved to obtain an approximate gaussion particle distribution size in the range of about. 10 to 20 ⁇ m. in diameter.
  • the ground material was then water washed and batch wise exchanged with 1M silver nitrate solution. Several exchanges were performed per patch until the silver- exchanged zeolite was about 15% by weight silver. After columns 71 were filled with the adsorbent, they were activated by heating to about 250° to 300° C for at least 4 hours with a slow purge of dry oxygen. At the conclusion of the heat treatment, the columns were cooled with a purge stream of dry nitrogen.
  • a xenon removal column 71 In operation, a xenon removal column 71 remains on-line receiving off-gases from line 55 until the column is loaded, or nearly so, at which time the off- gas stream is shifted to an alternate column 71. In most applications the xenon will not be radioactive; therefore, the gas may have some commercial value. Due to the relatively weak interaction between xenon and the selected adsorbent, when compared with H 2 O and CO 2 towards their respective adsorbents, the desorption temperature for xenon from column 71 is less, in the order of about 150° to 200° C.
  • the loaded column 71 is brought to the desorption temperature for xenon by external clamp heaters 72 and the adsorbed xenon is allowed to desorb for about 10 to 20 minutes before a heated back-purge gas flow through line 78 is commenced.
  • vent line 79 is closed and external water-cooled coils 73 utilized to cool the column back to adsorption temperature, about ambient.
  • forward-purged gas through the xenon removal columns 71 exits therefrom through lines 77 for recycling to dissolver unit 10 by way of line 42.
  • the off-gas exiting columns 71 primarily comprises major amounts of concentrated krypton and air. Because ozone is formed through radiolysis when oxygen is exposed to high radiation fields caused by concentrated krypton-85, and further because of the potential explosive hazard of ozone, it is preferred to maintain a low concentration level of oxygen. Therefore, the integrated process next includes means 90 for separating oxygen from the off-gas stream carried by line 75.
  • the teminology "oxygen removal means" is somewhat of a misnomer inasmuch as the gaseous component actually adsorbed therein is krypton. However, because the purpose of this step in the process is to effect the separation of oxygen from the off-gas stream, means 90 is accordingly identified by its intended purpose.
  • Oxygen separation means 90 comprising at least two adsorbent columns 91, or the like, are provided to receive off-gases from xenon removal means 70.
  • blower 80 and surge tank 81 are interposed therebetween. While the flow at this point is normally quite uniform, the addition of blower 80 and surge tank 81 prevent the propagation of any sudden surges of flow than may result from upsets in the upstream dissolver off-gas flow.
  • Oxygen separation is accomplished by selectively adsorbing krypton on silver-exchanged synthetic mordenite, the same adsorbent used within xenon removal columns 71, by utilizing the art-known technique of rapid cycle adsorption. While krypton does not interact strongly with the silver-exchanged mordenite at ambient temperature and pressure, krypton break through is inhibited a sufficient amount of time whereby to permit the majority of oxygen and nitrogen contained within the feed stream to pass through the columns 91. The weak interaction between krypton and the adsorbent material requires that the adsorption or feed cycle must be kept relatively short. The dimensions of oxygen separation columns 91 are such that the linear face velocity of the feed gas through the column is approximately 9.15 m./min.
  • the separation of krypton from oxygen can be effected as follows: (1) a feed or adsorption cycle time at about 8.0 m./min. linear face velocity for about 3.0 minutes, (2) a forward-purge cycle using nitrogen as the purge gas at about 16.0 m./min. for about 0.5 minutes, and (3) a back-purge or desorption cycle with nitrogen at about 16.0 m./min. linear face velocity through column 91 for about 2.5 minutes.
  • the forward-purge through purge line 94 sweeps residual oxygen from the adsorbent interstices within column 91 and is effective in removing oxygen because oxygen does not co-adsorb to any appreciable extent.
  • line 94 and column 91 discharge line 92 are closed and the column 91 vent line 96 and back-purge line 95 opened. Nitrogen is used for both the forward and back purge operations to prevent contamination of the recovered krypton with oxygen.
  • the back-purge flow from oxygen separation vent line 96 varies considerably during the oxygen separation cycles. Therefore, an additional blower 97 and surge tank 98 are used to ensure that the off-gas flow through feed line 100 to krypton separation means 110 is relatively uniform.
  • a flow regulator (not shown) is installed at the outlet of surge tank 98 for this purpose.
  • the average concentration of krypton in the krypton- nitrogen gas mixture exiting surge tank 98 is approximately 150 ppm.
  • the gas mixture is introduced into a cooler 99 to reduce its temperature to about -150° C.
  • the gas mixture is then introduced onto an adsorbent bed of silver-exchanged synthetic mordenite disposed within krypton separation columns 111. Columns 111 are cooled by coolers 113 to a temperature sufficient to adsorb krypton, about -140° to -160° C.
  • At least two krypton separation columns 111 are used, one for receiving the off-gas stream from line 100 while the other is in various stages of desorption or standby.
  • the column 111 diameter should be large enough to allow a linear face velocity of approximately 9.15 m./min. or less to obtain reasonably high loading times.
  • An alternative is to use longer adsorbent columns with higher face velocities to obtain equivalent loading times. Utilizing a face velocity of approximately 13.7 m./min. and a 1.525 m. long column, a loading time of about 3 hours is obtained when the adsorbent disposed within krypton separation columns 111 is maintained at about -140° to -160° C.
  • columns 111 The operation of columns 111 is as follows: The feed gas from surge tank 98 is initially cooled to about -150° C by passing said gas through a double-walled, liquid nitrogen cooled, coiled heat exchanger 99 prior to entering the on-line krypton separation column 111.
  • Line 100 is interlocked such that as the on-line column 111 feed line 100 is closed, the standby column 111 feed line 100 is opened.
  • the column 111 exit line 114 is similarly interlocked with the feed line 100 so that as the feed line 100 is closed, so too the exit line 114 on the same column 111 is closed.
  • the gas exiting a column 111 through line 114 is purified nitrogen and may be collected for reuse in a closed loop nitrogen recycle system such as hereafter described.
  • the respective vent line 116 is opened and heat is applied to the column by means of external plant heaters 112.
  • the back-purge line 115 is opened and a heated stream of nitrogen gas, heated by heater 119 to about 150° C, is used to back- purge the column 111.
  • Column 111 is heated and thus remains at about 150° C during the desorption cycle.
  • the back-purge flow rate is approximately 1/10th that of the adsorption or feed-flow rate.
  • the back-purge is continued until the desorbed krypton concentration exiting through vent line 116 is either approximately 200 ppm. or for a selected period of time.
  • the level of krypton concentration is less than about 0.5 ppm. In any event, this is insignificant inasmuch as the forward-purge flow is recycled back to blower 117 and surge tank 118.
  • the column 111 is cooled back down to the preferred krypton adsorption temperature by means of liquid nitrogen passing through cooling lines 113.
  • the process next provides means 130 for concentrating the krypton component of the gas carried by line 116 , said means comprising at least one krypton concentration column 131.
  • the desorbed krypton and nitrogen purge gas mixture from columns 111 is directed through a cooler 121 whereby to reduce the gas mixture temperature to about -140° C.
  • column 131 is discontinuous because there is only flow therein when the krypton separation columns 111 are back-purged. Therefore, the overall flow to column 131 is approximately 1/30th of that to the krypton separation columns 111. Also, only one column 131 is necessary. Because column 131 is required to accommodate only about 1/30th of the amount of flow to the krypton separation columns 111, the dimensions of column 131 are considerably less than those of columns 111. Column 131 diameter should be large enough to allow about a 9.15 m./min. face velocity therethrough because it contains therein the same silver-exchanged synthetic mordenite adsorbent. The adsorbent is cooled to about -140° to -160° C by means of liquid nitrogen passing through cooling lines 133. The length of column 131 is somewhat arbitrary and depends upon how many discharges from krypton separation columns 111 are desired per column 131 loading.
  • feed line 122 is opened when one of the krypton separation columns 111 back-purge vent lines 116 is opened.
  • the krypton concentration column 131 column exit line 134 is interlocked with the inlet line 122 so that as one opens or closes so does the other.
  • vent line 136 As column 131 becomes loaded, which may be after one or more discharges from krypton separation columns 111, the contents of column 131 are discharged through vent line 136 and directed to a krypton freeze-out trap 137.
  • inlet line 122 and outlet line 134 are closed, the back-purge vent line 135 is opened, and column 131 temperature raised by means of external clamp heaters 132 to approximately 150° C.
  • Nitrogen co-adsorbs with krypton at the low adsorption temperatures maintained within column 131 and desorbs at a lower temperature; therefore, as the column 131 temperature is raised the first gas to desrob, which is nitrogen, is directed through a by-pass valve 140 to line 138 for return to blower 80.
  • by-pass valve 140 redirects the gas flow to a krypton freeze-out trap 137 cooled to about -185° to -195° C. Most of the krypton and some of the nitrogen is collected in freeze-out trap 137 and the remaining gas recycled through line 138 back to blower 80.
  • nitrogen gas heated to about 150° C by heater 119, is used to back-purge the krypton gas to freeze-out trap 137 at a flow rate approximately 1/10th that of the column 131 loading rate.
  • Desorption is generally complete when the internal bed temperature of column 131 reaches about 150° C.
  • column 131 is isolated by closing back-purge line 135 and line 136 and the column is cooled to approximately -140° to -160° C with cooling coils 133 prior to the next adsorption or load cycle.
  • freeze-out trap 137 When the desorbed gas from krypton concentration column 131 has been collected in freeze-out trap 137, back-purge vent line 135 is closed and blower 117 is used to recycle any gaseous nitrogen or untrapped krypton.
  • freeze-out trap 137 When freeze-out trap 137 is warmed, the collected krypton can be transfered and/or compressed for steel cylinder 139 storage or other disposition.
  • Both the forward and back-purge of oxygen separation columns 91, and the back-purge for krypton separation columns 111 and krypton concentration column 131 utilize nitrogen from the recycle nitrogen surge tank 118. The only appreciable loss to the system is the 0.5 minute forward-purge to the oxygen separation columns 91.
  • the measurement sensitivities were about 0.1 ppm. for C0 2 and H 2 O, 0.5 ppm. for krypton and xenon, and about 10 ppm. for On.
  • concentrations in both cases would be several ppm. immediately after the column was put in service, then slowly decreased to below background until the beds were loaded. No significant amounts of krypton or xenon were measured in the H 2 O and CO 2 effluents during desorption.
  • the average CF for both the krypton separation and concentration columns were on the order of about 30 to 35 each, resulting in concentration of krypton to the freezeout trap on the order of about 1 to 20%.
  • the present invention has several important advantages over processes heretofore proposed and used for treatment of effluents from nuclear fuel reprocessing plants and other nuclear processes.
  • the process integrates each of the steps in such a way that each is compatible with the next.
  • the process does not introduce or result in a significant aqueous waste stream that may require additional treatment.
  • the separations are all effected at substantially ambient pressure and only the krypton separation and concentration steps require cryogenic cooling
  • the collected waste products are sufficiently concentrated to be acceptable for long term storage, though additional treatment will be necessary to convert the wastes to acceptable storage forms.
  • the decontamination factors resulting from the process are greater than those which are required or anticipated to meet existing and pending governmental regulations.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Methode d'extraction et de recuperation selective des gaz nobles et autres composants gazeux normalement emis pendant des operations de procedes nucleaires. Cette methode est adaptable et utile au traitement d'effluents de gaz de degagement emis pendant la regeneration de combustibles nucleaires epuises de facon a permettre une recuperation de matiere contaminante radioactive avant de liberer les gaz de degagement restants dans l'atmosphere. Brievement, cette methode comprend dans l'ordre le traitement des gaz de degagement pour extraire d'abord des composes organiques contenant du carbone, de l'hydrogene et du NOX, ainsi que des composes d'oxydes metalliques semi-volatiles produits par fission (11 et 16); l'adsorption des composants iodes sur de la mordenite a echange d'argent (17); l'extraction de la vapeur d'eau transportee par le courant au moyen d'un tamis moleculaire (31); l'extraction selective des composants de dioxyde de carbone dudit courant de gaz de degagement au moyen d'un tamis moleculaire (51); l'extraction selective du xenon en phase gazeuse en faisant passer le courant a travers un tamis moleculaire (71) comprenant de la mordenite a echange d'argent; la separation selective du krypton de l'ensemble du courant d'azote utilisant un tamis moleculaire (111) comprenant de la mordenite a echange d'argent refroidie a environ - 140 a - 160 C; la concentration du krypton desorbe sur un tamis moleculaire (131) comprenant de la mordenite a echange d'argent refroidie a environ - 140 a - 160 C; la concentration cryogenique ulterieure, et ensuite la recuperation pour stockage du krypton desorbe (137).
PCT/US1980/000992 1979-08-06 1980-08-06 Methode pour le traitement de courants gazeux emis pendant un procede nucleaire WO1981000413A1 (fr)

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AU62299/80A AU6229980A (en) 1979-08-10 1980-08-05 Timing apparatus for delaying opening of doors
DE19803049761 DE3049761A1 (de) 1979-08-06 1980-08-06 Method for treating a nuclear process off-gas stream

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US63970 1979-08-06

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2525804A1 (fr) * 1982-04-21 1983-10-28 Kernforschungsanlage Juelich Procede de separation du krypton d'un melange de gaz residuaire radioactif et installation pour executer ce procede
EP0332964A2 (fr) * 1988-03-16 1989-09-20 Bayer Ag Procédé pour l'élimination de l'iode et des composés de l'iode des gaz et des vapeurs en utilisant une zeolite X contenant de l'argent
WO1997019454A1 (fr) * 1995-11-17 1997-05-29 British Nuclear Fuels Plc Separation de gaz
US7594955B2 (en) * 2004-04-27 2009-09-29 Taiyo Nippon Sanso Corporation Process for recovering rare gases using gas-recovering container
WO2016005227A1 (fr) * 2014-07-08 2016-01-14 Clariant International Ltd Matériau d'adsorption servant à l'adsorption de gaz rares, utilisation dudit matériau et procédé d'adsorption de gaz rares
CN111681799A (zh) * 2020-04-30 2020-09-18 中国辐射防护研究院 一种放射性废树脂芬顿氧化废液干燥减容处理装置及方法
WO2022167669A1 (fr) * 2021-02-05 2022-08-11 Sck Cen Élimination d'un gaz rare radioactif d'un volume de gaz

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JP2011057491A (ja) * 2009-09-09 2011-03-24 Panasonic Corp ガス回収方法
CN102482088A (zh) * 2009-09-09 2012-05-30 松下电器产业株式会社 吸附材料和使用该吸附材料的氙吸附设备
ES2972484T3 (es) 2018-05-08 2024-06-13 Curium Us Llc Sistemas y métodos para la producción de xenón-133
CN115676786B (zh) * 2022-10-27 2024-04-19 江苏中科敬远节能科技有限公司 常温下基于银分子筛吸附的氦氖分离工艺

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US3476508A (en) * 1965-10-27 1969-11-04 Exxon Research Engineering Co Catalytic purification treatment of exhaust gas
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US3767764A (en) * 1971-12-09 1973-10-23 Grace W R & Co System for removing nitrogen oxide from automotive exhaust
US3944646A (en) * 1972-05-11 1976-03-16 Union Carbide Corporation Radioactive krypton gas separation
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US4087375A (en) * 1975-05-07 1978-05-02 Shin Tohoku Chemical Industry Co., Ltd. Method for treating radioactive waste water
US4093429A (en) * 1975-12-19 1978-06-06 General Electric Company Gas separation system
US4088737A (en) * 1976-11-02 1978-05-09 The United States Of America As Represented By The United States Department Of Energy Dry method for recycling iodine-loaded silver zeolite
US4201690A (en) * 1978-04-03 1980-05-06 United Kingdom Atomic Energy Authority Processing of irradiated nuclear fuel
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2525804A1 (fr) * 1982-04-21 1983-10-28 Kernforschungsanlage Juelich Procede de separation du krypton d'un melange de gaz residuaire radioactif et installation pour executer ce procede
GB2118761A (en) * 1982-04-21 1983-11-02 Kernforschungsanlage Juelich Separating krypton from a radioactive waste gas mixture
EP0332964A2 (fr) * 1988-03-16 1989-09-20 Bayer Ag Procédé pour l'élimination de l'iode et des composés de l'iode des gaz et des vapeurs en utilisant une zeolite X contenant de l'argent
EP0332964A3 (en) * 1988-03-16 1990-05-16 Bayer Ag Process for removal of iodine and iodine compounds from gases and vapours with silver containing zeolite x
WO1997019454A1 (fr) * 1995-11-17 1997-05-29 British Nuclear Fuels Plc Separation de gaz
US7594955B2 (en) * 2004-04-27 2009-09-29 Taiyo Nippon Sanso Corporation Process for recovering rare gases using gas-recovering container
WO2016005227A1 (fr) * 2014-07-08 2016-01-14 Clariant International Ltd Matériau d'adsorption servant à l'adsorption de gaz rares, utilisation dudit matériau et procédé d'adsorption de gaz rares
CN111681799A (zh) * 2020-04-30 2020-09-18 中国辐射防护研究院 一种放射性废树脂芬顿氧化废液干燥减容处理装置及方法
WO2022167669A1 (fr) * 2021-02-05 2022-08-11 Sck Cen Élimination d'un gaz rare radioactif d'un volume de gaz
EP4049743A1 (fr) * 2021-02-05 2022-08-31 Sck Cen Élimination d'un gaz noble radioactif d'un volume de gaz

Also Published As

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JPS56500976A (fr) 1981-07-16
GB2070454A (en) 1981-09-09
EP0032949A4 (fr) 1982-01-08
GB2070454B (en) 1983-12-07
EP0032949A1 (fr) 1981-08-05

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