DE2855650A1 - METHOD AND DEVICE FOR THE PYROHYDROLYTIC DECOMPOSITION OF HALOGENIC AND / OR PHOSPHORUS-CONTAINING ORGANIC SUBSTANCES - Google Patents
METHOD AND DEVICE FOR THE PYROHYDROLYTIC DECOMPOSITION OF HALOGENIC AND / OR PHOSPHORUS-CONTAINING ORGANIC SUBSTANCESInfo
- Publication number
- DE2855650A1 DE2855650A1 DE19782855650 DE2855650A DE2855650A1 DE 2855650 A1 DE2855650 A1 DE 2855650A1 DE 19782855650 DE19782855650 DE 19782855650 DE 2855650 A DE2855650 A DE 2855650A DE 2855650 A1 DE2855650 A1 DE 2855650A1
- Authority
- DE
- Germany
- Prior art keywords
- fluidized bed
- phosphorus
- calcium
- organic substances
- water vapor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 21
- 239000000126 substance Substances 0.000 title claims description 17
- 238000000354 decomposition reaction Methods 0.000 title claims description 7
- 239000007789 gas Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000004992 fission Effects 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- -1 calcium halide Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008263 liquid aerosol Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
Classifications
-
- 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
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/14—Processing by incineration; by calcination, e.g. desiccation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/32—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with introduction into the fluidised bed of more than one kind of moving particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Processing Of Solid Wastes (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Removal Of Specific Substances (AREA)
Description
NUKEM GmbH
6450 Hanau 11NUKEM GmbH
6450 Hanau 11
,f. Verfahren und Vorrichtung zur pyrohydrolytischen Zersetzung von Halogene und/oder Phosphor enthaltenden organischen Substanzen. , f. Method and device for the pyrohydrolytic decomposition of halogens and / or phosphorus-containing organic substances.
Die Erfindung betrifft ein Verfahren und eineThe invention relates to a method and a
Vorrichtung zur pyrohydrolytischen Zersetzung insbesondere kontaminierter organischer Substanzen, die Halogene (Cl, F, Br, J) und/oder Phosphor ent- ryc halten.Device for pyrohydrolytic decomposition, in particular of contaminated organic substances that contain halogens (Cl, F, Br, J) and / or phosphorus ent- ryc .
In der Nukleartechnik gibt es eine Reihe von kontaminierten organischen Lösungs- und Extraktionsmitteln, die beseitigt werden müssen. Besonders die In nuclear engineering there are a number of contaminated organic solvents and extractants that must be disposed of. Especially those
2Q Spaltprodukte aus kontaminierten Lösungen der Wiederaufarbeitung abgebrannter Kernbrennstoffe müssen gefahrlos isoliert und in endlagerfähige Form gebracht werden können. Hierzu gehört vor allem das hochaktive Extraktionsmittel aus der Wiederaufar» beitung, das zu 30 % aus Tributylphosphat (TRP) und Dodekan besteht. Aber auch im konventionellen Be-2Q fission products from contaminated reprocessing solutions Spent nuclear fuel must be isolated safely and brought into a form suitable for final disposal can be. Above all, this includes the highly active extractant from the recovery » processing that consists of 30% tributyl phosphate (TRP) and Dodecanese exists. But also in conventional
030029/0051030029/0051
reich gibt es Abfälle von chlorierten und fluorierten Lösungsmitteln, die nicht brennbar sind und in der Hitze sehr korrosive Salzsäure oder Flußsäure abspalten. Während man im radioaktiven Bereich bisher zwischenlagern musste, gab es im konventionellen Bereich hur die umweltfeindliche Beseitigung dieser Stoffe auf Hochsee-Verbrennungsschiffen.There is plenty of chlorinated and fluorinated waste Solvents that are non-flammable and split off very corrosive hydrochloric acid or hydrofluoric acid when heated. While in the radioactive area you previously had to store temporarily, there was in the conventional area Area hur the environmentally unfriendly disposal of these substances on deep-sea incineration ships.
Für kontaminierte organische Festabfälle ist ein Verfahren zur pyrohydrolytischen Veraschung bekannt (DE-OS 26 41 264), welches aber für halogenierte, insbesondere fluorierte organische Substanzen wegen des Auftretens der stark korrosiven Flußsäure nicht geeignet ist. Ebenso kann TBP auf diese Art nicht umgesetzt werden, weil dabei freie Phosphorsäure entsteht.A method for pyrohydrolytic incineration is known for contaminated organic solid waste (DE-OS 26 41 264), but which for halogenated, especially not fluorinated organic substances because of the occurrence of the highly corrosive hydrofluoric acid suitable is. Likewise, TBP cannot be converted in this way because it results in free phosphoric acid arises.
Zur Beseitigung von TBP ist ein spezielles Verfahren beschrieben worden (GB-PS 1 517 014), bei dem zunächst das TBP mit Phosphorsäure vom Dokekan abgetrenntA special process has been described for eliminating TBP (GB-PS 1 517 014), in which initially the TBP separated from the dokekan with phosphoric acid
2^ (Addukt-Verfahren) und dann das Addukt bei 1800C in Phosphorsäure und Buten zersetzt wird. Buten wird verbrannt, die hochaktive Phosphorsäure wird mit Kalkmilch gefällt und das entstehende Kalziumphosphat zur Endlagerung einbetoniert. Durch den Zusatz von 2 ^ (adduct method) and then the adduct is decomposed at 180 0 C in phosphoric acid and butene. Butene is burned, the highly active phosphoric acid is precipitated with milk of lime and the resulting calcium phosphate is concreted in for final storage. By adding
ow frischer Phosphorsäure entsteht bei diesem Verfahren zusätzlicher Abfall, so dass es sich bisher in der Praxis nicht durchsetzen konnte. ow fresh phosphoric acid is generated in this process additional waste, so that it has not been able to establish itself in practice up to now.
Es war daher Aufgabe der vorliegenden Erfindung, einIt was therefore an object of the present invention to provide a
Verfahren und eine Vorrichtung zur pyrohydrolytischenMethod and device for pyrohydrolytic
030029/OOSi ORIGINAL INSPECTED030029 / OOSi ORIGINAL INSPECTED
Zersetzung von Halogen und/oder Phosphor enthaltenden, insbesondere kontaminierten organischen Substanzen zu finden, die alle organischen Substanzgemische ohne vorherige Trennung und Rücksichtnahme auf korrosive Sekundärprodukte so beseitigen können, dass nur in-IQ aktive Abgase und ein gut weiter verarbeitbares, die Spaltprodukte einschliessendes anorganisches Produkt entstehen.Decomposition of halogen and / or phosphorus-containing, in particular contaminated organic substances find that all organic substance mixtures without prior separation and consideration of corrosive Can eliminate secondary products in such a way that only in-IQ active exhaust gases and an inorganic product that is easy to process and includes the fission products develop.
Diese Aufgabe wurde erfindungsgemäss dadurch gelöst, dass die Substanzen in eine mit Wasserdampf betriebenef aus granulatförmigen basischen Aluminium- und/oder Kalzium- und/oder Magnesiumverbindungen bestehende Wirbelschicht bei Temperaturen von 300 bis 8000C eingebracht werden. Dabei bilden die freigesetzten anorganischen Säuren, wie beispielsweise Flußsäure und Phosphorsäureffeste Salze mit dem Kalzium, dem Magnesium oder dem Aluminium. Bei der Pyrohydrolyse sich bildende Salzsäure lässt sich bei niederen Temperaturen ebenfalls zurückhalten, doch kann man sie bei höheren Temperaturen auch als HCl austreiben, was in einigen Fällen von Vorteil ist. Die Abgase aus diesem Prozess werden vorzugsweise in einer Nachbrennkammer bei etwa 10000C mit Sauerstoff oder Luft oxydiert, so dass nach eventueller Abscheidung von SaIzsäure in einem nachgeschalteten alkalischen Wäscher nach Kondensation des Wasserdampfes nur noch Kohlendioxid als Abgas übrigbleibt.This object has been achieved in that the substances are introduced in an operated with steam from f granular basic aluminum and / or calcium and / or magnesium compounds existing fluidized bed at temperatures of 300 to 800 0 C. The released inorganic acids such as hydrofluoric acid and phosphoric acid form f solid salts with calcium, magnesium or aluminum. Hydrochloric acid that forms during pyrohydrolysis can also be retained at lower temperatures, but it can also be driven off as HCl at higher temperatures, which is advantageous in some cases. The waste gases from this process are preferably oxidized in a secondary combustion chamber at about 1000 0 C with oxygen or air so that after optional separation of SaIzsäure in a subsequent alkaline scrubber after condensation of the water vapor only remains as carbon dioxide gas.
Vorzugsweise verwendet man für die Wirbelschicht ein Granulat aus Kalziuraoxid und/oder KalziumhydroxidGranules of calcium oxide and / or calcium hydroxide are preferably used for the fluidized bed
03002 970003002 9700
c doch sind auch beispielsweise Aluminiumoxid oder gebrannter Kalkstein anwendbar.c but are also, for example, aluminum oxide or burnt Limestone applicable.
Das erfindungsgemässe Verfahren der pyrohydrolytischen Zersetzung der Halogene und/oder Phosphor enthaltendenThe inventive method of pyrohydrolytic Decomposition of halogens and / or containing phosphorus
IQ organischen Substanzen ist ein endothermer Prozess. Er lässt sich deshalb sehr gut steuern. Dabei entstehen fast keine Flüssig-Aerosole, die Aktivität austragen könnten, sondern nur inaktive Gase. Die Spaltprodukte werden in die sich bildenden Aluminium- und/IQ organic substances is an endothermic process. It is therefore very easy to control. There are almost no liquid aerosols that can carry out activity could, but only inactive gases. The fission products are converted into the aluminum and /
■ic oder Kalzium- und/oder Magnesiumverbindungen eingeschlossen. ■ ic or calcium and / or magnesium compounds included.
Vorzugsweise wird das erfindungsgemässe Verfahren in einer Vorrichtung durchgeführt, die im wesentlichen aus einem Wirbelbettofen mit oder ohne Rührer besteht. Die Abbildung zeigt schematisch eine solche Vorrichtung.The method according to the invention is preferably carried out in carried out a device which consists essentially of a fluidized bed furnace with or without a stirrer. The figure shows such a device schematically.
Die organische Flüssigkeit wird über eine Zuleitung (l) in die Wirbelschicht (3) des Wirbelofens (2) bei 300 800 C eingespeist. Die gewünschte Umsetzungstemperatur wird durch den Heizmantel (9) und den überhitzten Wasserdampf, der über eine Zuleitung (5) eingebracht wird, sichergestellt. Als Wirbelsubstanz dient vorzugsweise Ca (0H)2/Ca0 - Granulat, als Wirbelgas dient der Wasserdampf. Die Einspeismenge an organischen Substanzen richtet sich nach der Wasserdampfmenge, das Verhältnis 2 Mol Wasserdampf zu 1 Mol hydrolysierbare Bindung in der organischen Substanz soll nicht unterschritten werden. Nach Umwandlung des CaO in Kalziumphosphat oderKalziumhalogenid kann der Bettinhalt über eine Leitung (4) abgelassen werden. Das Abgas, im wesent-The organic liquid is fed into the fluidized bed (3) of the fluidized bed furnace (2) at 300 800 C via a feed line (1). The desired reaction temperature is ensured by the heating jacket (9) and the superheated steam, which is introduced via a feed line (5). Ca (OH) 2 / Ca0 granulate is preferably used as the vortex substance, water vapor is used as the fluidizing gas. The amount of organic substances fed in depends on the amount of water vapor; the ratio should not fall below the ratio of 2 moles of water vapor to 1 mole of hydrolyzable bond in the organic substance. After the CaO has been converted into calcium phosphate or calcium halide, the contents of the bed can be drained off via a line (4). The exhaust gas, essentially
030029/0051030029/0051
c lichen Wasserdampf, Kohlenwasserstoffe., Kohlenmonoxid und Kohlendioxid passieren die rückblasbaren Filterkerzen (6) und werden vorzugsweise in einem Nachbrenner (7) mit überschüssigem Sauerstoff zu Wasser und CO2 verbrannt. Ein anschliessender Wäscher in (8) arbeitet bei ca. 1000C und pH = 5, wobei die eventuell entstandene Salzsäure absorbiert wird, C0„ und Wasserdampf entweichen können. Nach Rückhaltung der Aerosole an einem Tiefbettfaserfilter (lO) erfolgt die Kondensation des in den Abgasen enthaltenen Wasserte dampfes, der wieder in den Wirbelofen überführt wird. c union water vapor, hydrocarbons., carbon monoxide and carbon dioxide pass through the blow-back filter candles (6) and are preferably burned in an afterburner (7) with excess oxygen to form water and CO 2. A subsequent scrubber in (8) operates at approx. 100 ° C. and pH = 5, the hydrochloric acid that may be formed being absorbed, and CO 2 and water vapor can escape. After retention of the aerosols on a deep bed fiber filter (10), the condensation of the water vapor contained in the exhaust gases takes place, which is transferred back into the vortex furnace.
Folgende Beispiele sollen das erfindungsgemässe Verfahren näher erläutern:The following examples are intended to illustrate the process according to the invention explain in more detail:
2Q Beispiel 12Q example 1
In einem Wirbelbettofen befinden sich bei einer Temperatur von 4000C 60 kg CaO-Granulat. Als Wirbelgas wird auf 4000C überhitzter Wasserdampf (5Om5 n/h)In a fluidized bed furnace, at a temperature of 400 ° C., there are 60 kg of CaO granules. The fluidizing gas used is superheated steam (5Om 5 n / h) to 400 0 C.
benutzt.
25used.
25th
Unterhalb der Wirbelschicht wird ein mit hochangereichertem Uran kontaminiertes TBP/Kerosin (30/70)-Gemisch in einer Menge von 15 kg/h eingedüst. In dem mit 1000 C betriebenem Nachverbrenner werden 33m /h Sauerstoff zur vollständigen Umsetzung der Abgase zu COg und H2O eingespeist. Nach einem Betrieb von 36 Stunden ist die Wirbelschicht erschöpft und nicht mehr in der Lage, Phosphor aus dem TBP in Form von Phosphat zu binden. Sie muss abgezogenBelow the fluidized bed, a TBP / kerosene (30/70) mixture contaminated with highly enriched uranium is injected at a rate of 15 kg / h. In the afterburner operated at 1000 C, 33 m / h of oxygen are fed in to completely convert the exhaust gases to COg and H 2 O. After 36 hours of operation, the fluidized bed is exhausted and no longer able to bind phosphorus from the TBP in the form of phosphate. She must be withdrawn
-35 werden. Im Kreislaufwasser des Wäschers werden nur 0,02 % der in das Wirbelbett eingespeisten-35 to be. In the washer's circuit water, only 0.02 % is fed into the fluidized bed
030029/0051030029/0051
Aktivität wiedergefunden, während im Abgasabgang die radiometischen Messungen im Bereich des Nullpegels
liegen.Activity found again, while the radiometric measurements in the exhaust gas outlet were in the range of the zero level
lie.
In einem Wirbelbettofen, der sich auf einer Temperatur von 500 - 8000C befindet, werden 60 kg CaO-Granulat
vorgelegt. Als Wirbelgas werden 50m /h überhitzter Wasserdampf eingespeist. Unterhalb der Wirbelschicht
werden 15 kg Fluorkohlenwasserstoff (C0F0Cl.), das
mit hochangereichertem Uran kontaminiert ist, je
Stunde eingeschleust.In a fluidized bed furnace to a temperature of 500 - is 800 0 C, 60 kg CaO-granules are introduced. 50 m / h of superheated steam are fed in as fluidizing gas. Below the fluidized bed, 15 kg of fluorocarbon (C 0 F 0 Cl.), The
is contaminated with highly enriched uranium, ever
Hour.
Das , CaO in der Wirbelschicht ist 12 Stunden lang in der Lage, das aus dem Fluorkohlenwasserstoff freigesetzte
Fluor in Form von Kalziumfluorid zu binden.
Der freigesetzte Chlorwasserstoff wird bei diesen
Reaktionstemperaturen nicht gebunden, sondern entweicht über den Nachverbrenner in den bei pH = 5 gefahrenenThe CaO in the fluidized bed is able to bind the fluorine released from the fluorocarbon in the form of calcium fluoride for 12 hours. The released hydrogen chloride is in these
Reaction temperatures are not bound, but escapes via the afterburner into those at pH = 5
Wäscher, in dem das HCl absorbiert wird, während das 25Scrubber in which the HCl is absorbed while the 25th
in der Nachverbrennung entstandene CO0 den Wäscher CO 0 produced in the afterburning enters the scrubber
passiert. Der Nachverbrenner wird mit 4m /h Sauerstoff bei einer Temperatur von 100O0C betrieben.happened. The afterburner is operated at 4m / h oxygen at a temperature of 100O 0 C.
Im Kreislaufwasser des Wäschers befinden sich 0,03 % oU There are 0.03% oU in the washer's circuit water
der in das Wirbelbett eingespeisten Aktivität. Dasthe activity fed into the fluidized bed. That
gereinigte Abgas enthält lediglich noch Aktivität, die im Bereich des Nullpegels liegt.Purified exhaust gas only contains activity that is in the range of the zero level.
Frankfurt/Main, 19.12.1978Frankfurt / Main, December 19, 1978
Dr.Br.-BiDr.Br.-Bi
0 30029/00 51 ORIGI^ inspected0 30029/00 51 ORIGI ^ inspected
Claims (1)
6450 Hanau 11NUKEM GmbH
6450 Hanau 11
PATENT CLAIMS
mit Wasser gewaschen werden.Process according to claims 1 and 2, characterized in that the exhaust gases from the fluidized bed at about 100O 0 C nachverbrann
be washed with water.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2855650A DE2855650C2 (en) | 1978-12-22 | 1978-12-22 | Process for the pyrohydrolytic decomposition of phosphorus-containing liquids contaminated with highly enriched uranium |
| IT7968951A IT7968951A0 (en) | 1978-12-22 | 1979-10-08 | PROCEDURE AND DEVICE FOR THE PYROHYDROLYTIC DECOMPOSITION OF ORGANIC SUBSTANCES CONTAINING HALOGENS OR PHOSPHORUS |
| BE6/47043A BE880783A (en) | 1978-12-22 | 1979-12-20 | PROCESS AND DEVICE FOR THE PYROHYDROLYTIC DECOMPOSITION OF ORGANIC SUBSTANCES CONTAINING HALOGENS AND / OR PHOSPHORUS |
| BR7908390A BR7908390A (en) | 1978-12-22 | 1979-12-20 | PROCESS AND DEVICE FOR PIROHYDROLYTIC DISINTAGATION OF ORGANIC SUBSTANCES CONTAINING HALOGENE AND / OR PHOSPHORUS |
| GB7943906A GB2039774A (en) | 1978-12-22 | 1979-12-20 | A Process and an Apparatus for the Pyrohydrolytic Decomposition of Organic Substances Containing Halogens and/or Phosphorus |
| JP16577979A JPS5587099A (en) | 1978-12-22 | 1979-12-21 | Method and device for decomposing organic material containing halogen and or phosphor by high heat hydrolysis |
| FR7931513A FR2444496A1 (en) | 1978-12-22 | 1979-12-21 | PROCESS AND PLANT FOR THE PYROHYDROLYTIC DECOMPOSITION OF ORGANIC SUBSTANCES CONTAINING HALOGENS AND / OR PHOSPHORUS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2855650A DE2855650C2 (en) | 1978-12-22 | 1978-12-22 | Process for the pyrohydrolytic decomposition of phosphorus-containing liquids contaminated with highly enriched uranium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2855650A1 true DE2855650A1 (en) | 1980-07-17 |
| DE2855650C2 DE2855650C2 (en) | 1984-10-25 |
Family
ID=6058106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2855650A Expired DE2855650C2 (en) | 1978-12-22 | 1978-12-22 | Process for the pyrohydrolytic decomposition of phosphorus-containing liquids contaminated with highly enriched uranium |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5587099A (en) |
| BE (1) | BE880783A (en) |
| BR (1) | BR7908390A (en) |
| DE (1) | DE2855650C2 (en) |
| FR (1) | FR2444496A1 (en) |
| GB (1) | GB2039774A (en) |
| IT (1) | IT7968951A0 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044991A1 (en) * | 1980-07-25 | 1982-02-03 | Nukem GmbH | Process and device for the pyrolytic destruction of organic substances that contain halogens and/or phosphor |
| DE3443722A1 (en) * | 1984-11-30 | 1986-06-12 | Foerster Guenther | Process for the thermal disposal of halogen compounds, in particular wastes containing chlorine compounds forming dioxins, phosgene and polychlorinated biphenyls and fluidised-bed reactor for carrying it out |
| EP0188718A1 (en) * | 1984-12-24 | 1986-07-30 | Nukem GmbH | Process for the chemical-thermal decomposition of higher halogenated hydrocarbons |
| DE3604318A1 (en) * | 1986-02-12 | 1987-08-13 | Metallgesellschaft Ag | METHOD FOR BURNING COW MIST |
| DE4021309A1 (en) * | 1989-09-01 | 1991-03-07 | Delta T Ingenieurtechnik & App | Process thermally breaking down chemical and treating toxic residues - has number of indirectly heated fluidised bed incinerators used in series to provide efficient disposal of harmful chemicals |
| DE4118123A1 (en) * | 1991-06-03 | 1992-12-10 | Siemens Ag | METHOD AND DEVICE FOR TREATING A RADIOACTIVE WASTE SOLUTION |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410126A (en) * | 1978-10-12 | 1983-10-18 | Cooper Industries, Inc. | Mass soldering system |
| CA1163431A (en) * | 1982-08-20 | 1984-03-13 | Atomic Energy Of Canada Limited - Energie Atomique Du Canada, Limitee | Method of reducing the volume of radioactive waste |
| JPS59107300A (en) * | 1982-12-10 | 1984-06-21 | 株式会社日立製作所 | Method of processing radioactive resin waste |
| CA1294111C (en) * | 1986-08-08 | 1992-01-14 | Douglas J. Hallett | Process for the destruction of organic waste material |
| JPS63171398A (en) * | 1987-01-09 | 1988-07-15 | 日本碍子株式会社 | Method and device for processing radioactive waste |
| JPH04115390U (en) * | 1991-03-29 | 1992-10-13 | アイワ株式会社 | Electronics |
| US20160379727A1 (en) * | 2015-01-30 | 2016-12-29 | Studsvik, Inc. | Apparatus and methods for treatment of radioactive organic waste |
| DE102015115119A1 (en) * | 2015-09-09 | 2017-03-09 | Wehrle-Werk Ag | Process for phosphorus recovery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB837967A (en) * | 1956-11-30 | 1960-06-15 | Atomic Energy Commission | Method of handling radio active waste solutions |
| DE2056096A1 (en) * | 1970-11-14 | 1972-06-15 | Metallgesellschaft Ag | Process for the separation of hydrogen fluoride |
| DE2641264A1 (en) * | 1976-09-14 | 1978-03-16 | Nukem Gmbh | PROCEDURES FOR DISPOSAL OF RADIOACTIVE ORGANIC WASTE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1495622A (en) * | 1966-08-12 | 1967-09-22 | Commissariat Energie Atomique | Fluorinated organic liquids incineration process |
| US3907674A (en) * | 1974-04-24 | 1975-09-23 | Dorr Oliver Inc | Fluid bed incineration of wastes containing alkali metal chlorides |
| BE819818A (en) * | 1974-09-12 | 1974-12-31 | METHOD OF TREATING ORGANIC WASTE |
-
1978
- 1978-12-22 DE DE2855650A patent/DE2855650C2/en not_active Expired
-
1979
- 1979-10-08 IT IT7968951A patent/IT7968951A0/en unknown
- 1979-12-20 BR BR7908390A patent/BR7908390A/en unknown
- 1979-12-20 GB GB7943906A patent/GB2039774A/en not_active Withdrawn
- 1979-12-20 BE BE6/47043A patent/BE880783A/en unknown
- 1979-12-21 FR FR7931513A patent/FR2444496A1/en not_active Withdrawn
- 1979-12-21 JP JP16577979A patent/JPS5587099A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB837967A (en) * | 1956-11-30 | 1960-06-15 | Atomic Energy Commission | Method of handling radio active waste solutions |
| DE2056096A1 (en) * | 1970-11-14 | 1972-06-15 | Metallgesellschaft Ag | Process for the separation of hydrogen fluoride |
| DE2641264A1 (en) * | 1976-09-14 | 1978-03-16 | Nukem Gmbh | PROCEDURES FOR DISPOSAL OF RADIOACTIVE ORGANIC WASTE |
Non-Patent Citations (2)
| Title |
|---|
| Chemie, Ingenieur, Technik, 50, 1978, Nr. 9, S. 662-669 * |
| Fortschritte der Verfahrenstechnik, Bd. 14, 1976, S. 592 und 593 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044991A1 (en) * | 1980-07-25 | 1982-02-03 | Nukem GmbH | Process and device for the pyrolytic destruction of organic substances that contain halogens and/or phosphor |
| US4711185A (en) * | 1980-07-25 | 1987-12-08 | Nukem Gmbh | Process and apparatus for the decomposition of halogen and/or phosphoric containing organic materials |
| DE3443722A1 (en) * | 1984-11-30 | 1986-06-12 | Foerster Guenther | Process for the thermal disposal of halogen compounds, in particular wastes containing chlorine compounds forming dioxins, phosgene and polychlorinated biphenyls and fluidised-bed reactor for carrying it out |
| EP0188718A1 (en) * | 1984-12-24 | 1986-07-30 | Nukem GmbH | Process for the chemical-thermal decomposition of higher halogenated hydrocarbons |
| DE3604318A1 (en) * | 1986-02-12 | 1987-08-13 | Metallgesellschaft Ag | METHOD FOR BURNING COW MIST |
| US4747356A (en) * | 1986-02-12 | 1988-05-31 | Metallgesellschaft Ag | Process of burning cattle dung |
| DE4021309A1 (en) * | 1989-09-01 | 1991-03-07 | Delta T Ingenieurtechnik & App | Process thermally breaking down chemical and treating toxic residues - has number of indirectly heated fluidised bed incinerators used in series to provide efficient disposal of harmful chemicals |
| DE4118123A1 (en) * | 1991-06-03 | 1992-12-10 | Siemens Ag | METHOD AND DEVICE FOR TREATING A RADIOACTIVE WASTE SOLUTION |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2444496A1 (en) | 1980-07-18 |
| IT7968951A0 (en) | 1979-10-08 |
| DE2855650C2 (en) | 1984-10-25 |
| GB2039774A (en) | 1980-08-20 |
| BE880783A (en) | 1980-06-20 |
| JPS5587099A (en) | 1980-07-01 |
| BR7908390A (en) | 1980-10-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OAR | Request for search filed | ||
| OC | Search report available | ||
| OD | Request for examination | ||
| 8125 | Change of the main classification |
Ipc: B01J 8/24 |
|
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8327 | Change in the person/name/address of the patent owner |
Owner name: NUKEM GMBH, 8755 ALZENAU, DE |
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| 8339 | Ceased/non-payment of the annual fee |