WO1993004209A1 - Process and plant for recovering heavy metals from waste - Google Patents
Process and plant for recovering heavy metals from waste Download PDFInfo
- Publication number
- WO1993004209A1 WO1993004209A1 PCT/EP1992/001891 EP9201891W WO9304209A1 WO 1993004209 A1 WO1993004209 A1 WO 1993004209A1 EP 9201891 W EP9201891 W EP 9201891W WO 9304209 A1 WO9304209 A1 WO 9304209A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- chamber
- gas
- waste
- evaporation
- evaporation chamber
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/50—Destroying solid waste or transforming solid waste into something useful or harmless involving radiation, e.g. electro-magnetic waves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
Definitions
- the invention relates to a method for the recovery of heavy metals, in particular mercury, lead or cadmium from adsorbents, scrap, building rubble or soil, in which the adsorbents or waste are in a treatment chamber under a vacuum of one
- Inert gas are flowed around and heated, the gases containing heavy metal vapor arising in the treatment chamber being passed into a post-combustion chamber and heavy metal1 emerging from the exhaust gas emerging therefrom being condensed, and one
- the Adsorptions ⁇ can z. B. activated carbon, activated coke, carbon molecular sieves, zeolitic molecular sieves, plastic molecular sieves, aluminum oxide, silica gel, zeolites, diatomaceous earth.
- Such a method for the recovery of mercury is known from DE-A 32 43 813.
- the temperature in the treatment chamber is increased in stages, so that only discontinuous operation is possible.
- the object of the invention is to improve the methods of the type mentioned so that a continuous disposal of waste such as scrap, building rubble, soil and. The like. is possible by separating out heavy metals contained therein, the plant for carrying out the method being intended to make it easy to adapt to the case to be processed in terms of control technology.
- the object is achieved with respect to the method by the characterizing features of claim 1 and with respect to the system for carrying out the method by means of the characterizing features of
- the system 1 according to FIG. 1 consists of a degassing chamber 2, a high temperature chamber 14, an evaporation chamber 21 and a freezer device 20.
- the degassing chamber 2 has a conveyor device 5, by means of which waste introduced via the entry lock 3 can be conveyed through the degassing chamber 2 to a discharge lock 4.
- a conveyor 29 is assigned to the conveyor device 5, so that the weight of the material contaminated with heavy metals, such as, for. B. mercury batteries can be weighed continuously during the task.
- An arrangement of radiators 6 is provided above the conveyor device 2. By means of these radiators 6, the atmosphere in the degassing chamber 2 is heated to 250 ° C. by the energy of the electromagnetic waves introduced.
- a connection piece 7 is provided, to which an inert gas container 10 is connected by means of a line 8 with valve 9.
- the inert gas container 10 can, for. B. filled with N2.
- the inert gas flows through the degassing chamber 2 and is enriched with vapors escaping from the waste.
- Plastic-containing impurities contained in the waste such as long-chain hydrocarbon compounds or chlorinated hydrocarbons, are completely evaporated in the degassing chamber 2.
- the material slowly migrates to the material delivery section 30 of the conveyor device 5.
- This process is ended after a throughput time t which is dependent on the dissipation energy entered and the evaporable plastic parts.
- the required throughput time and the amount of dissipation energy to be contributed is determined by determined a computer, not shown, by which the valves 9, 13 and the radiator 6 are controlled.
- the emitters 6 are preferably operated to emit infrared radiation in the wavelength range from 1 mm to 780 nm.
- an exhaust pipe 11 is provided, to which a high-temperature chamber 14 is connected by means of a line 12 with valve 13.
- the high temperature chamber 14 has a burner 15 which, for. B. can be operated with propane.
- Baffles 16 are arranged downstream of the combustion chamber and serve to direct the gas mixture consisting of combustion exhaust gases and the inert gas which has been drawn off from the degassing chamber 2 and enriched with gaseous impurities.
- the burner 15 is preferably set such that a gas temperature of approximately 1400 ° C. is present in the area of the baffles 16. This makes it possible to split vapors of the wastes absorbed by the inert gas in the molecular range, so that the
- the high temperature splitting is preferably supported by introducing ozone into the combustion chamber.
- an ozone generator 31 can be connected to line 12.
- the reaction process of the splitting is accelerated by the ozone and can thus be carried out more efficiently.
- This treatment of the exhaust gas drawn off from the degassing chamber 2 means that the gas mixture emerging from the high-temperature chamber 14 can be completely inert.
- This self-inerting makes it possible to operate the evaporation chamber 21 without supplying nitrogen, but at least to limit the proportion of nitrogen to be supplied to the inert gas circuit 23 of the evaporation chamber 21.
- a heat exchanger 17 is provided, through which the gas mixture emerging from the baffles 16 flows.
- a line 18 with a fan 19 is connected, which is connected to a freezer 20.
- the gas emerging from the high-temperature chamber 14 can reach z. B. - 30 ° C to be cooled.
- the heavy metal vapor condenses out and can be fed to a heavy metal condensate container (not shown in more detail).
- the gas mixture cleaned of heavy metal vapor can be released into the atmosphere after further filtration, if necessary.
- degassed waste is introduced into the evaporation chamber 21 via the discharge lock 4.
- the waste is also subjected to electromagnetic wave energy by means of an arrangement 22 of emitters 32. It is advantageous to emit radiators 32 with alternating ones in the feed direction of the waste
- the evaporation chamber 21 is flowed through by an inert gas, preferably heated to 510 ° C., of the inert gas circuit 23 already mentioned.
- the inert gas sucked out of the evaporation chamber 21 by means of a blower 28 flows through a preheater 24 by being heated to approximately 357 ° C.
- the preheater 24 is connected to the heat exchanger 17 of the high temperature chamber 14.
- the inert gas flows from the preheater 24 in a heavy metal vapor separator 25.
- the heavy metal vapor is fed to the deep-freeze device 20, while the inert gas cleaned of heavy metal vapor flows through line 27 through a heat exchanger 26 in order to re-enter the evaporation chamber 21 after heating to 510 ° C. .
- the emitters 32 can emit electromagnetic wave energy in the high-frequency range (100 kHz to MHz range), in the medium-frequency range (0.15 to 20 kHz) or in the low-frequency range ( ⁇ 50 to 60 kHz) to 900 ° C. It is also possible to carry out this heating up to 900 ° C. by means of electromagnetic wave energy in the infrared range.
- the evaporation chamber 21 can also be surrounded by a combustion chamber fired with gas or oil, by means of which the material located in the evaporation chamber 21 is heated to 900 ° C.
- a slide 36, 37 is arranged at the entrance and exit of the evaporation chamber 21, by means of which the evaporation chamber 21 can be closed in a manner which is resistant to negative and positive pressure. Unexpected pressure peaks occurring in this evaporation chamber 21 are intercepted by a pressure relief valve 45.
- inert gas is forced through the evaporation chamber 21 by a blower 28. The gas heated in this absorbs heavy metal vapors which are discharged from the evaporation chamber 21 with the purge gas stream.
- the gas volume increasing due to the heavy metal evaporation is discharged and extracted with the aid of an ejector 46.
- the slides 36, 37 can be designed as rotary slides or rotary locks, whereby a fully automatic loading of the evaporation chamber 21 is possible. If batch operation is provided, the slides 36, 37 can be designed as flat slides.
- the cleaned waste material emerging from the outlet lock 33 is conveyed through a conveyor
- FIGS. 3 and 4 Such an embodiment is shown in FIGS. 3 and 4 for the systems 41, 42.
- the ejector 46 with frozen gas of z. B. - 30 ° C, for which a fan 48 is provided. As soon as the cold gas flow with that withdrawn from the second stage of the vaporization chamber 21
- This separator 35 can be used as a cyclone or
- the ejector 46 is operated with frozen liquid 52, which, for. B. mercury, brine, heat exchange oil, liquid nitrogen or the like. May be.
- This liquid 52 is pumped from a reservoir 53 by means of a pump 54 via a heat exchanger 55 in the circuit and in the heat exchanger 55 to z. B.> - 30 ° C cooled.
- the frozen liquid 52 is fed from the collecting container 53 to the ejector 46 by means of a pump 56 and injected therein.
- exhaust gas from the high-temperature chamber 14 is fed to the ejector 46.
- the condensate is separated in the separator 35 and returned to the collecting container 53 with the liquid of the ejector jet.
- the gas flow from the ejector 35 consisting of steam and gas residues is passed through a heat exchanger 57 arranged above the separator 35 and released into the atmosphere via a filter 38.
- a heat exchanger 57 z. B. the mercury from the gas current contained mixture of moisture and metal vapor by freezing to z. B. - 30 ° C and fed to the collection container 53.
- Excess liquid 52 such as. B. mercury in the system 42 of FIG. 4 in the collecting container 53 is discharged into another container 62.
- the evaporation chamber 21 can also be made inert by means of the exhaust gas from the high-temperature chamber 14, from which a partial flow is returned to the evaporation chamber 21 by means of a fan 58.
- the liquid 69 which contains mercury and is recirculated through the heat exchanger 55 and recooled to ⁇ 30 ° C., can also be introduced directly into the feed line 68 of the ejector 46.
- FIG. 5 shows a further embodiment of a system 43 which is particularly suitable for the decontamination of mercury-containing material. If exhaust gas emerging from the high-temperature chamber 14 has to be discharged into the atmosphere, it is filtered through a filter 38 with a
- Adsorbent performed.
- This adsorbent can e.g. B. be activated carbon. It is also possible to use carbon molecular sieves or zeolitic molecular sieves or plastic molecular sieves. Aluminum oxide, silica gel, zeolites and silica can also be used.
- the entry lock 3 there is a mill 60.
- mercury-containing wastes are ground under liquid nitrogen at temperatures below ⁇ 41 ° C.
- the frozen regrind is then introduced into the degassing chamber 2 via the entry lock 3 and in this on z. B. heated to 280 ° C.
- the resulting inert gas mixture with plastic vapors is pumped off to the high-temperature chamber 14 and is broken down therein, as already described above.
- a partial flow of the exhaust gas from the high temperature chamber 14 is via the filter 38 in the Atmosphere.
- the residual gas is reintroduced into the degassing chamber 2 via the fan 59.
- a pump 61 presses liquid mercury from the collecting container 62 into the evaporation chamber 21 before the evaporation chamber 21 is heated up, until the latter is filled.
- the pump 61 circulates mercury in the evaporation chamber 21 while the latter is being heated to approximately 200.degree. This forms Hg, Ag, Au-containing amalgam, which is pumped into the deposition chamber 39 by means of the pump 63.
- the amalgam is freed of mercury by heating the mixture to about 800 ° C.
- the deposition chamber 39 is evacuated by means of the vacuum pump 64.
- the mercury evaporates and is in the freezer 20 designed as a condenser by recooling to z. B. - 30 ° C condensed and collected in the collecting container 62.
- Au-Ag residues are removed by opening the slide 65.
- Residual scrap such as steel and coal scrap remaining in the evaporation chamber 21 is discharged after the amalgam has been completely removed and the remaining residual material has been heated to approximately 800.degree.
- residual mercury is evaporated and fed to the freezer 20 by means of a fan 66 and condensed. This mercury condensate is also discharged into the container 62.
- the residual scrap is then applied to the conveyor 47 by opening a screen slide 67 and a slide slide 68. It is possible to remove the material from the chamber 39 in the wet process, e.g. B. further digest in a nitric acid bath.
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Abstract
Description
Verfahren und Anlage zur Rückgewinnung von Schwermetall aus Abfällen Process and plant for the recovery of heavy metal from waste
Die Erfindung betrifft ein Verfahren zur Rückgewinnung von Schwermetallen insbesondere Quecksilber, Blei oder Cadmium aus Adsorptionsmitteln, Schrott, Bauschutt oder Erdreich, bei dem die Adsorptionsmittel oder Abfälle in einer Behandlungskammer unter Unterdruck von einemThe invention relates to a method for the recovery of heavy metals, in particular mercury, lead or cadmium from adsorbents, scrap, building rubble or soil, in which the adsorbents or waste are in a treatment chamber under a vacuum of one
Inertgas umströmt und erhitzt werden, wobei die in der Behandlungskammer entstehenden Schwermetalldampf enthal¬ tenden Gase in eine Nachverbrennungskammer geleitet werden und aus dem aus dieser austretenden Abgas Schwer- metal1 durch Kondensation rückgewonnen wird, und eineInert gas are flowed around and heated, the gases containing heavy metal vapor arising in the treatment chamber being passed into a post-combustion chamber and heavy metal1 emerging from the exhaust gas emerging therefrom being condensed, and one
Anlage zur Durchführung des Verfahrens. Die Adsorptions¬ mittel können z. B. Aktivkohle, Aktivkoks, Kohlenstoff- molekularsiebe, zeolithische Molekularsiebe, Kunstoff- olekularsiebe, Aluminiumoxid, Silicagel, Zeolithe, Kie- selgur sein.Plant for carrying out the process. The Adsorptions¬ can z. B. activated carbon, activated coke, carbon molecular sieves, zeolitic molecular sieves, plastic molecular sieves, aluminum oxide, silica gel, zeolites, diatomaceous earth.
Ein derartiges Verfahren für die Rückgewinnung von Quecksilber ist durch die DE-A 32 43 813 bekannt. Hier¬ bei wird die Temperatur in der Behandlungskammer in Stufen erhöht, so daß nur ein diskontinuierlicher Be¬ trieb möglich ist. Die Aufgabe der Erfindung besteht darin, daß Verfahren der eingangs genannten Art so zu verbessern, daß eine kontinuierliche Entsorgung von Abfällen wie Schrott, Bauschutt, Erdreich u. dgl. durch Ausscheiden von in diesen enthaltenen Schwermetallen möglich ist, wobei die Anlage zur Durchführung des Ver¬ fahrens eine regelungstechnische einfach Anpassung an den jeweils aufzubereitenden Fall ermöglichen soll.Such a method for the recovery of mercury is known from DE-A 32 43 813. In this case, the temperature in the treatment chamber is increased in stages, so that only discontinuous operation is possible. The object of the invention is to improve the methods of the type mentioned so that a continuous disposal of waste such as scrap, building rubble, soil and. The like. is possible by separating out heavy metals contained therein, the plant for carrying out the method being intended to make it easy to adapt to the case to be processed in terms of control technology.
Erfindungsgemäß erfolgt die Lösung der Aufgabe bezüglich des Verfahrens durch die kennzeichnenden Merkmale des Anspruchs 1 und bezüglich der Anlage zur Durchführung des Verfahrens durch die kennzeichnenden Merkmale desAccording to the invention, the object is achieved with respect to the method by the characterizing features of claim 1 and with respect to the system for carrying out the method by means of the characterizing features of
ERSATZBLATT Anspruchs 16 .REPLACEMENT LEAF Claim 16.
Die Erfindung wird nachfolgend am Beispiel der in der Zeichnungen sche atisch dargestellten Anlagen näher erläutert.The invention is explained in more detail below using the example of the systems shown schematically in the drawings.
Die Anlage 1 nach Fig. 1 besteht aus einer Entgasungs¬ kammer 2, einer Hochtemperaturkammer 14, einer Ver¬ dampfungskammer 21 sowie einer Tiefkühleinrichtung 20.The system 1 according to FIG. 1 consists of a degassing chamber 2, a high temperature chamber 14, an evaporation chamber 21 and a freezer device 20.
Die Entgasungskammer 2 weist eine Fördereinrichtung 5 auf, mittels derer über die Eintragschleuse 3 einge¬ brachter Abfall durch die Entgasungskammer 2 bis zu einer Austragschleuse 4 gefördert werden kann. Der För- dereinrichtung 5 ist eine Waage 29 zugeordnet, so daß das Gewicht des mit Schwermetallen kontaminierten Guts wie z. B. Quecksilberbatterien während der Gutaufgabe kontinuierlich gewogen werden kann. Oberhalb der Förder¬ einrichtung 2 ist eine Anordnung von Strahlern 6 vorge- sehen. Mittels dieser Strahler 6 wird durch die Energie der eingebrachten elektromagnetischen Wellen die At¬ mosphäre in der Entgasungskammer 2 auf 250° C aufge¬ heizt. Vor der Eintragschleuse 3 ist ein Anschlußstutzen 7 vorgesehen, an den mittels einer Leitung 8 mit Ventil 9 ein Inertgasbehälter 10 angeschlossen ist. Der Inert¬ gasbehälter 10 kann z. B. mit N2 gefüllt sein. Das Inertgas strömt durch die Entgasungskammer 2 und wird hierbei mit aus den Abfällen entweichenden Dämpfen ange¬ reichert. In den Abfällen enthaltene kunststoffhaltige Verunreinigungen wie langkettige KohlenwasserstoffVerbin¬ dungen bzw. Chlorkohlenwasserstoffe werden in der Ent¬ gasungskammer 2 vollständig verdampft. Hierbei wandert das Gut langsam bis zum Gutabgabeabschnitt 30 der För¬ dereinrichtung 5. Dieser Vorgang wird nach einer Durch- laufzeit t beendet, die von der eingetragenen Dissipa- tionsenergie und den verdampfungsfähigen Kunststoffan¬ teilen abhängig ist. Die erforderliche Durchlaufzeit und der einzubringende Dissipationsenergiebetrag wird von einem nicht näher dargestellten Rechner ermittelt, durch den auch die Ventile 9, 13 und die Strahler 6 gesteuert werden. Die Strahler 6 werden vorzugsweise zur Emission von Infrarotstrahlung im Wellenlängenbereich von 1 mm bis 780 nm betrieben. Am Ende der Entgasungskammer 2 ist ein Abgasstutzen 11 vorgesehen, an dem mittels einer Leitung 12 mit Ventil 13 eine Hochtemperaturkammer 14 angeschlossen ist.The degassing chamber 2 has a conveyor device 5, by means of which waste introduced via the entry lock 3 can be conveyed through the degassing chamber 2 to a discharge lock 4. A conveyor 29 is assigned to the conveyor device 5, so that the weight of the material contaminated with heavy metals, such as, for. B. mercury batteries can be weighed continuously during the task. An arrangement of radiators 6 is provided above the conveyor device 2. By means of these radiators 6, the atmosphere in the degassing chamber 2 is heated to 250 ° C. by the energy of the electromagnetic waves introduced. In front of the entry lock 3, a connection piece 7 is provided, to which an inert gas container 10 is connected by means of a line 8 with valve 9. The inert gas container 10 can, for. B. filled with N2. The inert gas flows through the degassing chamber 2 and is enriched with vapors escaping from the waste. Plastic-containing impurities contained in the waste, such as long-chain hydrocarbon compounds or chlorinated hydrocarbons, are completely evaporated in the degassing chamber 2. In this case, the material slowly migrates to the material delivery section 30 of the conveyor device 5. This process is ended after a throughput time t which is dependent on the dissipation energy entered and the evaporable plastic parts. The required throughput time and the amount of dissipation energy to be contributed is determined by determined a computer, not shown, by which the valves 9, 13 and the radiator 6 are controlled. The emitters 6 are preferably operated to emit infrared radiation in the wavelength range from 1 mm to 780 nm. At the end of the degassing chamber 2, an exhaust pipe 11 is provided, to which a high-temperature chamber 14 is connected by means of a line 12 with valve 13.
Die Hochtemperaturkammer 14 weist einen Brenner 15 auf, der z. B. mit Propan betrieben werden kann. Im Anschluß an die Brennkammer sind Schikanen 16 angeordnet, die zur U lenkung des aus Verbrennungsabgasen und dem aus der Entgasungskammer 2 abgezogenen mit gasförmigen Verun- reinigungen angereicherten Inertgas bestehenden Gasge¬ misches dienen. Der Brenner 15 wird vorzugsweise so eingestellt, daß im Bereich der Schikanen 16 eine Gas¬ temperatur von etwa 1400° C vorliegt. Hierdurch ist es möglich, von dem Inertgas aufgenommene Dämpfe der Ab- fälle im molekularen Bereich zu spalten, so daß dieThe high temperature chamber 14 has a burner 15 which, for. B. can be operated with propane. Baffles 16 are arranged downstream of the combustion chamber and serve to direct the gas mixture consisting of combustion exhaust gases and the inert gas which has been drawn off from the degassing chamber 2 and enriched with gaseous impurities. The burner 15 is preferably set such that a gas temperature of approximately 1400 ° C. is present in the area of the baffles 16. This makes it possible to split vapors of the wastes absorbed by the inert gas in the molecular range, so that the
Entfernung umweltschädigender Bestandteile durch Aufspal¬ tung der Kohlenwasserstoff-und Chlorkohlenwasserstoffan¬ teile vereinfacht wird. Vorzugsweise wird die Hochtem¬ peraturspaltung durch Einführung von Ozon in die Brenn- ka mer unterstützt. Hierzu kann an die Leitung 12 ein Ozonerzeuger 31 angeschlossen werden. Durch das Ozon wird der Reaktionsablauf der Aufspaltung beschleunigt und kann somit effizienter durchgeführt werden. Durch diese Behandlung des aus der Entgasungskammer 2 abge- zogenen Abgases kann das aus der Hochtemperaturkammer 14 austretende Gasgemisch vollständig inertisiert sein. Durch diese Eigeninertisierung ist es möglich, die Ver¬ dampfungskammer 21 ohne Zufuhr von Stickstoff zu be¬ treiben, zumindest aber den Anteil des dem Inertgas- kreislauf 23 der Verdampfungskammer 21 zuzuführenden Stickstoffs zu begrenzen.Removal of environmentally harmful components is simplified by splitting the hydrocarbon and chlorohydrocarbon components. The high temperature splitting is preferably supported by introducing ozone into the combustion chamber. For this purpose, an ozone generator 31 can be connected to line 12. The reaction process of the splitting is accelerated by the ozone and can thus be carried out more efficiently. This treatment of the exhaust gas drawn off from the degassing chamber 2 means that the gas mixture emerging from the high-temperature chamber 14 can be completely inert. This self-inerting makes it possible to operate the evaporation chamber 21 without supplying nitrogen, but at least to limit the proportion of nitrogen to be supplied to the inert gas circuit 23 of the evaporation chamber 21.
ERSATZBLATT In Strömungsrichtung hinter den Schikanen 16 ist ein Wärmetauscher 17 vorgesehen, der von dem aus den Schi¬ kanen 16 austretenden Gasgemisch durchströmt wird. Am Ausgang der Hochtemperaturkammer 14 ist eine Leitung 18 mit einem Gebläse 19 angeschlossen, die mit einer Tief- kühleinrichtung 20 verbunden ist. In dieser Tiefkühlein- richtung 20 kann das aus der Hochtemperaturkammer 14 austretende Gas auf z. B. - 30° C abgekühlt werden. Hierbei kondensiert der Schwermetalldampf aus und kann einem nicht näher dargestellten Schwermetallkondensat¬ behälter zugeführt werden. Das von Schwermetalldampf gereinigte Gasgemisch kann nach ggf. einer weiteren Fil¬ trierung in die Atmosphäre ausgelassen werden.REPLACEMENT LEAF In the direction of flow behind the baffles 16, a heat exchanger 17 is provided, through which the gas mixture emerging from the baffles 16 flows. At the outlet of the high-temperature chamber 14, a line 18 with a fan 19 is connected, which is connected to a freezer 20. In this deep-freeze device 20, the gas emerging from the high-temperature chamber 14 can reach z. B. - 30 ° C to be cooled. The heavy metal vapor condenses out and can be fed to a heavy metal condensate container (not shown in more detail). The gas mixture cleaned of heavy metal vapor can be released into the atmosphere after further filtration, if necessary.
In der Entgasungskammer 2 entgaster Abfall wird über die Austragschleuse 4 in die Verdampfungskammer 21 einge¬ bracht. Hierbei wird der Abfall ebenfalls mittels einer Anordnung 22 von Strahlern 32 mit elektromagnetischer Wellenenergie beaufschlagt. Von Vorteil ist es, in Vor- schubrichtung des Abfalls Strahler 32 mit wechselndenIn the degassing chamber 2, degassed waste is introduced into the evaporation chamber 21 via the discharge lock 4. Here, the waste is also subjected to electromagnetic wave energy by means of an arrangement 22 of emitters 32. It is advantageous to emit radiators 32 with alternating ones in the feed direction of the waste
Frequenzen einzusetzen, da hierdurch der Abfall leichter aufgeschlossen werden kann. Entgegengesetzt zur Vor¬ schubrichtung des Abfalls wird die Verdampfungskammer 21 von einem vorzugsweise auf 510° C erwärmtem Inertgas des bereits erwähnten Inertgaskreislaufs 23 durchströmt. Das aus der Verdampfungskammer 21 mittels eines Gebläses 28 abgesaugte Inertgas durchströmt einen Vorerhitzer 24, indem es auf ca. 357° C erwärmt wird. Der Vorerhitzer 24 ist mit dem Wärmetauscher 17 der Hochtemperaturkammer 14 verbunden. Aus dem Vorerhitzer 24 strömt das Inertgas in einem Schwermetalldampfabscheider 25. Der Schwermetall¬ dampf wird der Tiefkühleinrichtung 20 zugeführt, während das um Schwermetalldampf gereinigte Inertgas über die Leitung 27 einen Wärmetauscher 26 durchströmt, um nach Erwärmung auf 510° C wieder in die Verdampfungskammer 21 einzutreten.Use frequencies because this makes it easier to digest the waste. Contrary to the direction of advance of the waste, the evaporation chamber 21 is flowed through by an inert gas, preferably heated to 510 ° C., of the inert gas circuit 23 already mentioned. The inert gas sucked out of the evaporation chamber 21 by means of a blower 28 flows through a preheater 24 by being heated to approximately 357 ° C. The preheater 24 is connected to the heat exchanger 17 of the high temperature chamber 14. The inert gas flows from the preheater 24 in a heavy metal vapor separator 25. The heavy metal vapor is fed to the deep-freeze device 20, while the inert gas cleaned of heavy metal vapor flows through line 27 through a heat exchanger 26 in order to re-enter the evaporation chamber 21 after heating to 510 ° C. .
ERSATZBLATT Abhängig von der Zusammensetzung des durch die Austrag¬ schleuse 4 in die Verdampfungskammer 21 eingebrachten Abfalls können die Strahler 32 mit elektromagnetischer Wellenenergie im Hochfrequenzbereich (100 kHz bis MHz- Bereich), im Mittelfrequenzbereich (0,15 bis 20 kHz) oder im Niederfrequenzbereich ( ≤ 50 bis 60 kHz) bis 900° C erwärmt werden. Es ist auch möglich, diese Erwär¬ mung bis 900° C mittels elektromagnetischer Wellen¬ energie im Infrarotbereich durchzuführen. Alternativ oder ergänzend kann die Verdampfungskammer 21 auch von einem mit Gas oder Öl befeuerten Brennraum umgeben sein, durch den das in der Verdampfungskammer 21 befindliche Gut auf 900° C erwärmt wird.ER S ATZBLATT Depending on the composition of the waste introduced into the evaporation chamber 21 through the discharge lock 4, the emitters 32 can emit electromagnetic wave energy in the high-frequency range (100 kHz to MHz range), in the medium-frequency range (0.15 to 20 kHz) or in the low-frequency range (≤ 50 to 60 kHz) to 900 ° C. It is also possible to carry out this heating up to 900 ° C. by means of electromagnetic wave energy in the infrared range. Alternatively or additionally, the evaporation chamber 21 can also be surrounded by a combustion chamber fired with gas or oil, by means of which the material located in the evaporation chamber 21 is heated to 900 ° C.
Sofern ein kontinuierlicher chargenweiser Betrieb durch¬ geführt werden soll, ist es von Vorteil, vor der Austrag¬ schleuse 4 der Entgasungskammer 2 einen Zwischenspeicher 34 vorzusehen, wie es bei der in Fig. 2 dargestellten Anlage 40 gezeigt ist. Am Eingang und Ausgang der Ver- dampfungskammer 21 ist jeweils ein Schieber 36, 37 an¬ geordnet, durch den die Verdampfungskammer 21 unter- und überdruckfest verschlossen werden kann. In dieser Ver¬ dampfungskammer 21 auftretende unvorhergesehene Druck¬ spitzen werden durch ein Überdruckventil 45 abgefangen. Während des gesamten Verdampfungsprozesses wird durch ein Gebläse 28 Inertgas durch die Verdampfungskammer 21 gedrückt. Das in dieser angeheizte Gas nimmt Schwerme¬ talldämpfe auf, die mit dem Spülgasstrom aus der Ver¬ dampfungskammer 21 ausgetragen werden. Das durch die Schwermetallverdampfung zunehmende Gasvolumen wird ab¬ geführt und mit Hilfe eines Ejektors 46 abgesaugt. Die Schieber 36, 37 können als Rotationsschieber oder Dreh¬ schleusen ausgebildet sein, wodurch eine vollautoma¬ tische Beschickung der Verdampfungskammer 21 möglich ist. Sofern ein chargenweiser Betrieb vorgesehen ist, können die Schieber 36, 37 als Flachschieber ausgebildet sein. Das aus der Auslaßschleuse 33 austretende ge¬ reinigte Abfallmaterial wird über eine FördereinrichtungIf continuous batch operation is to be carried out, it is advantageous to provide an intermediate store 34 in front of the discharge lock 4 of the degassing chamber 2, as is shown in the system 40 shown in FIG. 2. A slide 36, 37 is arranged at the entrance and exit of the evaporation chamber 21, by means of which the evaporation chamber 21 can be closed in a manner which is resistant to negative and positive pressure. Unexpected pressure peaks occurring in this evaporation chamber 21 are intercepted by a pressure relief valve 45. During the entire evaporation process, inert gas is forced through the evaporation chamber 21 by a blower 28. The gas heated in this absorbs heavy metal vapors which are discharged from the evaporation chamber 21 with the purge gas stream. The gas volume increasing due to the heavy metal evaporation is discharged and extracted with the aid of an ejector 46. The slides 36, 37 can be designed as rotary slides or rotary locks, whereby a fully automatic loading of the evaporation chamber 21 is possible. If batch operation is provided, the slides 36, 37 can be designed as flat slides. The cleaned waste material emerging from the outlet lock 33 is conveyed through a conveyor
ERSATZBLATT 47 abgeführt.REPLACEMENT LEAF 47 removed.
Es ist möglich, die Verdampfungskammer 21 mehrstufig auszubilden. Eine solche Ausführung ist in den Fig. 3 und 4 zu den Anlagen 41, 42 gezeigt.It is possible to design the evaporation chamber 21 in several stages. Such an embodiment is shown in FIGS. 3 and 4 for the systems 41, 42.
Bei der Anlage 41 wird der Ejektor 46 mit tiefgekühltem Gas von z. B. - 30° C betrieben, wozu ein Gebläse 48 vorgesehen ist. Sobald der Kaltgasstrom mit dem aus der zweiten Stufe der Verdampfungskammer 21 abgezogenenIn the system 41, the ejector 46 with frozen gas of z. B. - 30 ° C, for which a fan 48 is provided. As soon as the cold gas flow with that withdrawn from the second stage of the vaporization chamber 21
Quecksilberdampf in Berührung kommt, findet eine sofor¬ tige Kondensation der ausgegasten Bestandteile statt. Die so entstehenden Kondensattrσpfchen werden im Ab-, scheider 35 abgeschieden und einem Kondensatsammler 49 zugeführt. Dieser Abscheider 35 kann als Zyklon oderIf mercury vapor comes into contact, an immediate condensation of the outgassed components takes place. The resulting condensate droplets are separated in the separator 35 and fed to a condensate collector 49. This separator 35 can be used as a cyclone or
Multizyklon ausgebildet sein. Durch die Abscheidung der Kondensattröpfchen wird verhindert, daß sich die nach¬ geschalteten Wärmetauscher 50, 51 zusetzen.Be multicyclone. The separation of the condensate droplets prevents the downstream heat exchangers 50, 51 from becoming clogged.
Bei der Anlage 42 wird der Ejektor 46 mit tiefgekühlter Flüssigkeit 52 betrieben, die z. B. Quecksilber, Sole, Wärmetauscheröl, flüssiger Stickstoff od. dgl. sein kann. Diese Flüssigkeit 52 wird aus einem Sammelbehälter 53 mittels einer Pumpe 54 über einen Wärmetauscher 55 im Kreislauf gepumpt und in dem Wärmetauscher 55 auf z. B. > - 30° C abgekühlt. Aus dem Sammelbehälter 53 wird die tiefgekühlte Flüssigkeit 52 mittels einer Pumpe 56 dem Ejektor 46 zugeführt und in diesen eingespritzt. Gleich¬ zeitig wird dem Ejektor 46 Abgas aus der Hochtemperatur- kammer 14 zugeführt. Hierbei tritt im EjektorstrahlIn the system 42, the ejector 46 is operated with frozen liquid 52, which, for. B. mercury, brine, heat exchange oil, liquid nitrogen or the like. May be. This liquid 52 is pumped from a reservoir 53 by means of a pump 54 via a heat exchanger 55 in the circuit and in the heat exchanger 55 to z. B.> - 30 ° C cooled. The frozen liquid 52 is fed from the collecting container 53 to the ejector 46 by means of a pump 56 and injected therein. At the same time, exhaust gas from the high-temperature chamber 14 is fed to the ejector 46. Here occurs in the ejector jet
Kondensatbildung auf. Das Kondensat wird im Abscheider 35 abgeschieden und mit der Flüssigkeit des Ejektor- εtrahls in den Sammelbehälter 53 zurückgeführt. Der aus dem Ejektor 35 austretende Gasstrom aus Dampf- und Gas- resten wird durch einen oberhalb des Abscheiders 35 angeordneten Wärmetauscher 57 geleitet und über einen Filter 38 in die Atmosphäre ausgelassen. In dem Wärme¬ tauscher 57 wird z. B. das Quecksilber aus dem im Gas- ström enthaltenen Gemisch aus Feuchtigkeit und Metall¬ dampf durch Tiefkühlμng auf z. B. - 30°C abgeschieden und dem Sammelbehälter 53 zugeführt. Überschüssige Flüs¬ sigkeit 52 wie z. B. Quecksilber bei der Anlage 42 nach Fig. 4 in dem Sammelbehälter 53 wird in einen weiteren Behälter 62 abgeführt. Bei dieser Anlage 42 kann die Inertisierung der Verdampfungskammer 21 auch mittels des Abgases der Hochtemperaturkammer 14 erfolgen, von der ein Teilstrom in die Verdampfungskammer 21 mittels eines Gebläses 58 zurückgeführt wird. Wie in Fig. 4 durch eine Strichlinie angedeutet, kann die durch den Wärmetauscher 55 geleitete und auf - 30° C rückgekühlte Flüssigkeit 69, die Quecksilber enthält, auch direkt in die Vorlauf¬ leitung 68 des Ejektors 46 eingeführt werden.Formation of condensate. The condensate is separated in the separator 35 and returned to the collecting container 53 with the liquid of the ejector jet. The gas flow from the ejector 35 consisting of steam and gas residues is passed through a heat exchanger 57 arranged above the separator 35 and released into the atmosphere via a filter 38. In the heat exchanger 57 z. B. the mercury from the gas current contained mixture of moisture and metal vapor by freezing to z. B. - 30 ° C and fed to the collection container 53. Excess liquid 52 such as. B. mercury in the system 42 of FIG. 4 in the collecting container 53 is discharged into another container 62. In this system 42, the evaporation chamber 21 can also be made inert by means of the exhaust gas from the high-temperature chamber 14, from which a partial flow is returned to the evaporation chamber 21 by means of a fan 58. As indicated by a dashed line in FIG. 4, the liquid 69, which contains mercury and is recirculated through the heat exchanger 55 and recooled to −30 ° C., can also be introduced directly into the feed line 68 of the ejector 46.
Fig. 5 zeigt eine weitere Ausgestaltung einer Anlage 43, die besonders zur Dekontaminierung von quecksilberhal¬ tigem Gut geeignet ist. Soweit aus der Hochtemperatur¬ kammer 14 austretendes Abgas in die Atmosphäre abgelei- tet werden muß, wird es durch ein Filter 38 mit einem5 shows a further embodiment of a system 43 which is particularly suitable for the decontamination of mercury-containing material. If exhaust gas emerging from the high-temperature chamber 14 has to be discharged into the atmosphere, it is filtered through a filter 38 with a
Adsorptionsmittel geführt. Dieses Adsorptionsmittel kann z. B. Aktivkohle sein. Es ist auch möglich, Kohlenstoff- molekularsiebe oder zeolithische Molekularsiebe oder Kunststoff olekularsiebe zu verwenden. Ferner kann auch Aluminiumoxid, Silicagel, Zeolithe und Kieseldioxid ver¬ wendet werden.Adsorbent performed. This adsorbent can e.g. B. be activated carbon. It is also possible to use carbon molecular sieves or zeolitic molecular sieves or plastic molecular sieves. Aluminum oxide, silica gel, zeolites and silica can also be used.
Oberhalb der Eintragschleuse 3 befindet sich eine Mühle 60. In dieser werden im Tieftemperaturverfahren bei Temperaturen unter - 41° C unter flüssigem Stickstoff quecksilberhaltige Abfälle zermahlen. Das tiefgekühlte Mahlgut wird dann über die Eintragschleuse 3 in die Entgasungskammer 2 eingebracht und in dieser auf z. B. 280° C erwärmt. Das hierbei entstehende inerte Gasge- misch mit Kunststoffdämpfen wird zur Hochtemperatur¬ kammer 14 abgepumpt und in dieser wie bereits oben be¬ schrieben zerlegt. Ein Teilstrom des Abgases aus der Hochtemperaturkammer 14 wird über das Filter 38 in die Atmosphäre geleitet. Das Restgas wird über das Gebläse 59 wieder in die Entgasungskammer 2 eingeleitet.Above the entry lock 3 there is a mill 60. In this cryogenic process, mercury-containing wastes are ground under liquid nitrogen at temperatures below −41 ° C. The frozen regrind is then introduced into the degassing chamber 2 via the entry lock 3 and in this on z. B. heated to 280 ° C. The resulting inert gas mixture with plastic vapors is pumped off to the high-temperature chamber 14 and is broken down therein, as already described above. A partial flow of the exhaust gas from the high temperature chamber 14 is via the filter 38 in the Atmosphere. The residual gas is reintroduced into the degassing chamber 2 via the fan 59.
Das in der Entgasungskammer 2 entgaste Mahlgut gelangt über die Austragschleuse 4 in die Verdampfungskammer 21. Eine Pumpe 61 drückt vor dem Aufheizen der Verdampfungs¬ kammer 21 flüssiges Quecksilber aus dem Sammelbehälter 62 in die Verdampfungskammer 21, bis diese aufgefüllt ist. Mittels der Pumpe 61 zirkuliert Quecksilber in der Verdampfungskammer 21 während diese auf etwa 200° C aufgeheizt wird. Hierbei bildet sich Hg, Ag, Au-haltiges Amalgam, das mittels der Pumpe 63 in die Abscheidekammer 39 gepumpt wird. Hier wird das Amalgam von Quecksilber befreit, in dem das Gemisch auf etwa 800° C erwärmt wird. Während des Heizens wird mittels der Vakuumpumpe 64 die Abscheidekammer 39 evakuiert. Das Quecksilber verdampft und wird in der als Kondensator ausgebildeten Tiefkühleinrichtung 20 durch Rückkühlung auf z. B. - 30° C kondensiert und im Sammelbehälter 62 aufgefangen. Au-Ag-Reste werden durch Öffnen des Schiebers 65 ausge¬ tragen.The ground material degassed in the degassing chamber 2 reaches the evaporation chamber 21 via the discharge lock 4. A pump 61 presses liquid mercury from the collecting container 62 into the evaporation chamber 21 before the evaporation chamber 21 is heated up, until the latter is filled. The pump 61 circulates mercury in the evaporation chamber 21 while the latter is being heated to approximately 200.degree. This forms Hg, Ag, Au-containing amalgam, which is pumped into the deposition chamber 39 by means of the pump 63. Here the amalgam is freed of mercury by heating the mixture to about 800 ° C. During heating, the deposition chamber 39 is evacuated by means of the vacuum pump 64. The mercury evaporates and is in the freezer 20 designed as a condenser by recooling to z. B. - 30 ° C condensed and collected in the collecting container 62. Au-Ag residues are removed by opening the slide 65.
In der Verdampfungskammer 21 verbliebener Restschrott wie Stahl- und Kohlenschrott wird ausgetragen, nach dem das Amalgam vollständig abgezogen und das verbliebene Restmaterial auf ca. 800° C aufgeheizt wurde. Hierbei wird Restquecksilber verdampft und mittels eines Ge¬ bläses 66 der Tiefkühleinrichtung 20 zugeführt und kon¬ densiert. Auch diese Quecksilberkondensat wird in den Behälter 62 abgeleitet. Der Restschrott wird dann durch Öffnen eines Siebschiebers 67 und eines Verschlußschie¬ bers 68 auf die Fördereinrichtung 47 aufgetragen. Es ist möglich, das Gut aus der Kammer 39 im Naßverfahren z. B. in einem Salpetersäurebad weiter aufzuschließen. Residual scrap such as steel and coal scrap remaining in the evaporation chamber 21 is discharged after the amalgam has been completely removed and the remaining residual material has been heated to approximately 800.degree. Here, residual mercury is evaporated and fed to the freezer 20 by means of a fan 66 and condensed. This mercury condensate is also discharged into the container 62. The residual scrap is then applied to the conveyor 47 by opening a screen slide 67 and a slide slide 68. It is possible to remove the material from the chamber 39 in the wet process, e.g. B. further digest in a nitric acid bath.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4127506A DE4127506C1 (en) | 1991-08-20 | 1991-08-20 | |
| DEP4127506.3 | 1991-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993004209A1 true WO1993004209A1 (en) | 1993-03-04 |
Family
ID=6438676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/001891 Ceased WO1993004209A1 (en) | 1991-08-20 | 1992-08-18 | Process and plant for recovering heavy metals from waste |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4127506C1 (en) |
| WO (1) | WO1993004209A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522518A (en) * | 2020-12-01 | 2021-03-19 | 昆明理工大学 | Safe control and comprehensive recycling method for high-lead mercury-containing acid mud |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4339794C2 (en) * | 1993-11-16 | 1996-07-11 | Werec Gmbh Berlin Wertstoff Re | Process for the treatment of waste / residues containing amalgam |
| DE4405398C1 (en) * | 1994-02-21 | 1995-04-27 | Nordische Quecksilber Rueckgew | Process and device for continuous thermal removal of mercury from luminescent material |
| EP0857520A1 (en) * | 1997-02-06 | 1998-08-12 | Akzo Nobel N.V. | Treatment of contaminated soil |
| FR2917312A1 (en) * | 2007-06-15 | 2008-12-19 | Ct Internat De Traitement Et D | METHOD FOR PROCESSING MERCURY WASTE AND INSTALLATION FOR ITS IMPLEMENTATION |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704875A (en) * | 1971-07-01 | 1972-12-05 | Pennwalt Corp | Removal of mercury from effluent streams |
| GB1524464A (en) * | 1975-05-05 | 1978-09-13 | Anic Spa | Purification of mercury-containing sludges |
| DE3243813A1 (en) * | 1981-12-01 | 1983-07-07 | Lumalampan Ab, Karlskrona | METHOD AND DEVICE FOR RECOVERY OF MERCURY |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3816282C1 (en) * | 1988-05-12 | 1989-10-05 | Gerhard Dipl.-Ing. 6940 Weinheim De Bernecker |
-
1991
- 1991-08-20 DE DE4127506A patent/DE4127506C1/de not_active Expired - Fee Related
-
1992
- 1992-08-18 WO PCT/EP1992/001891 patent/WO1993004209A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704875A (en) * | 1971-07-01 | 1972-12-05 | Pennwalt Corp | Removal of mercury from effluent streams |
| GB1524464A (en) * | 1975-05-05 | 1978-09-13 | Anic Spa | Purification of mercury-containing sludges |
| DE3243813A1 (en) * | 1981-12-01 | 1983-07-07 | Lumalampan Ab, Karlskrona | METHOD AND DEVICE FOR RECOVERY OF MERCURY |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522518A (en) * | 2020-12-01 | 2021-03-19 | 昆明理工大学 | Safe control and comprehensive recycling method for high-lead mercury-containing acid mud |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4127506C1 (en) | 1992-10-15 |
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