EP0635283A1 - Process for the reductive dehalogenation of solid and liquid materials containing organohalogens - Google Patents
Process for the reductive dehalogenation of solid and liquid materials containing organohalogens Download PDFInfo
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- EP0635283A1 EP0635283A1 EP94250184A EP94250184A EP0635283A1 EP 0635283 A1 EP0635283 A1 EP 0635283A1 EP 94250184 A EP94250184 A EP 94250184A EP 94250184 A EP94250184 A EP 94250184A EP 0635283 A1 EP0635283 A1 EP 0635283A1
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- Prior art keywords
- sodium
- solid
- ammonia
- minutes
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40
Definitions
- the invention relates to a chemical process for the dehalogenation of halogenated hydrocarbons which are contained in mixtures of solid or liquid substances.
- Waste or by-products of industrial processes which contain organically bound halogens (fluorine, chlorine, bromine, iodine as organohalogens or halogenated hydrocarbons) represent a considerable risk potential because of their ecotoxic properties. Numerous processes are known for their destruction and z. T. technically tested (see G. Dehoust, Ch. Ewen, R. Gensicke: waste factory, shown using the example of the disposal of organic halogen waste, waste and refuse 1991 (5), 283-294).
- Lissel and Fründ provide a current overview of available non-thermal processes ⁇ M. Lissel, M. Fründ, Labor 2000, 1991, 205 - 208Ü. After the Degussa sodium process DE-PS 28 13 200 C2 (1978), US Pat. 4 255 252 (1979) Sodium as a suspension (average 20 particle diameter below 100 ⁇ m, preferably below 30 ⁇ m) in oil at elevated temperatures (90-160 ° C) reacted with pretreated waste oils.
- An advantage of this sodium process is its selectivity. In contrast to oxidative degradation and catalytic hydrogenation, hydrocarbons are not affected. Because of its high reactivity, sodium can cause complete dehalogenation even at low temperatures and short reaction times, provided that there is no transport limitation in the reaction medium.
- the technical implementation of the sodium process requires a comparatively low investment and is therefore particularly suitable for smaller, possibly mobile systems.
- An obvious disadvantage of using metal suspensions is that solid products cannot be easily treated with them because solid-solid reactions have a high inhibition of transport. It is precisely this application which is of interest for the treatment of solids such as loaded activated carbons and cokes, filter dusts and others in which there are low concentrations of more or less bound hydrogen halides on a solid matrix.
- the invention solves the problem of making halogenated hydrocarbons, which are sorbed on solid matrices, available for direct dehalogenation with sodium without the need for an additional extraction step.
- the contaminated solid is arranged in a fixed bed and a sodium solution in ammonia flows through it.
- the treatment can be carried out at temperatures near the boiling point of ammonia under atmospheric pressure or at temperatures near ambient temperature under elevated pressure or under conditions between these corner points.
- solvent ammonia can either be removed as a liquid phase from the purified solid or evaporated directly.
- the evaporation is achieved depending on the reaction conditions by heating and / or relaxing. In any case, the ammonia is circulated.
- Reaction temperatures above 30 ° C only make sense if this is to cause additional effects on the solid matrix (e.g. extraction of further pollutants).
- the processing of the reaction products depends on the chosen embodiment and the waste product to be cleaned. It contains the following steps, which can be combined in different ways: (i) decomposition of excess sodium by adding water or other reagents with active hydrogen (e.g. methanol, acetic acid, dilute mineral acids or the like); (ii) evaporation of the solvent by heating or decompression, the evaporated ammonia being recycled after liquefaction; (iii) washing and neutralizing the cleaned solid or wash water, if necessary.
- active hydrogen e.g. methanol, acetic acid, dilute mineral acids or the like
Abstract
Description
Die Erfindung betrifft ein chemisches Verfahren zur Dehalogenierung von Halogenkohlenwasserstoffen, die in Gemischen von festen oder flüssigen Stoffen enthalten sind. Abfälle oder Nebenprodukte industrieller Prozesse, die organisch gebundene Halogene (Fluor, Chlor, Brom, Iod als Organohalogene oder Halogenkohlenwasserstoffe) enthalten, stellen wegen ihrer ökotoxischen Eigenschaften ein erhebliches Gefahrenpotential dar. Für ihre Zerstörung sind zahlreiche Verfahren bekannt und z. T. technisch erprobt (siehe G. Dehoust, Ch. Ewen, R. Gensicke: Abfallfabrik, dargestellt am Beispiel der Beseitigung halogenorganischer Abfälle, Müll und Abfall 1991 (5), 283-294). Als Alternative zur Hochtemperaturverbrennung oder Hochtemperaturpyrolyse sind Verfahren zur reduktiven Dehalogenierung unter milden Reaktionsbedingungen von Interesse. Lissel und Fründ geben eine aktuelle Übersicht über verfügbare nichtthermische Verfahren ÄM. Lissel, M. Fründ, Labor 2000, 1991, 205 - 208Ü. Nach dem Degussa- Natrium-Prozeß DE-PS 28 13 200 C2 (1978), US-Pat. 4 255 252 (1979) wird Natrium als Suspension (mittlerer 20 Teilchendurchmesser unter 100 µm, vorzugsweise unter 30 µm) in Öl bei erhöhten Temperaturen (90 - 160 °C) mit vorbehandelten Abfallölen zur Reaktion gebracht.The invention relates to a chemical process for the dehalogenation of halogenated hydrocarbons which are contained in mixtures of solid or liquid substances. Waste or by-products of industrial processes which contain organically bound halogens (fluorine, chlorine, bromine, iodine as organohalogens or halogenated hydrocarbons) represent a considerable risk potential because of their ecotoxic properties. Numerous processes are known for their destruction and z. T. technically tested (see G. Dehoust, Ch. Ewen, R. Gensicke: waste factory, shown using the example of the disposal of organic halogen waste, waste and refuse 1991 (5), 283-294). Processes for reductive dehalogenation under mild reaction conditions are of interest as an alternative to high-temperature combustion or high-temperature pyrolysis. Lissel and Fründ provide a current overview of available non-thermal processes ÄM. Lissel, M. Fründ, Labor 2000, 1991, 205 - 208Ü. After the Degussa sodium process DE-PS 28 13 200 C2 (1978), US Pat. 4 255 252 (1979) Sodium as a suspension (average 20 particle diameter below 100 µm, preferably below 30 µm) in oil at elevated temperatures (90-160 ° C) reacted with pretreated waste oils.
Ein Vorteil dieses Natrium-Prozesses ist seine Selektivität. Im Unterschied zum oxidativen Abbau und zur katalytischen Hydrierung werden Kohlenwasserstoffe davon nicht betroffen. Wegen seiner hohen Reaktivität kann Natrium bereits bei niedrigen Temperaturen und kurzen Reaktionszeiten eine vollständige Dehalogenierung bewirken, sofern keine Transportlimitierung im Reaktionsmedium auftritt. Die technische Umsetzung des Natrium-Prozesses erfordert einen vergleichsweise geringen Investitionsaufwand und ist daher für kleinere, ggf. mobile Anlagen besonders geeignet. Ein offensichtlicher Nachteil der Anwendung von Metallsuspensionen besteht darin, daß feste Produkte damit nicht in einfacher Weise behandelt werden können, weil Feststoff-Feststoff-Reaktionen eine hohe Transporthemmung aufweisen. Eben diese Anwendung ist aber von Interesse für die Behandlung von Feststoffen wie beladenen Aktivkohlen und -koksen, Filterstäuben u. a., bei denen geringe Konzentrationen von mehr oder weniger festgebundenen Halogenwasserstoffen auf einer festen Matrix vorliegen.An advantage of this sodium process is its selectivity. In contrast to oxidative degradation and catalytic hydrogenation, hydrocarbons are not affected. Because of its high reactivity, sodium can cause complete dehalogenation even at low temperatures and short reaction times, provided that there is no transport limitation in the reaction medium. The technical implementation of the sodium process requires a comparatively low investment and is therefore particularly suitable for smaller, possibly mobile systems. An obvious disadvantage of using metal suspensions is that solid products cannot be easily treated with them because solid-solid reactions have a high inhibition of transport. It is precisely this application which is of interest for the treatment of solids such as loaded activated carbons and cokes, filter dusts and others in which there are low concentrations of more or less bound hydrogen halides on a solid matrix.
Die Erfindung löst die Aufgabe, Halogenkohlenwasserstoffe, die an festen Matrices sorbiert vorliegen, einer direkten Dehalogenierung mit Natrium zugänglich zu machen, ohne daß dafür ein zusätzlicher Extraktionsschritt erforderlich wird.The invention solves the problem of making halogenated hydrocarbons, which are sorbed on solid matrices, available for direct dehalogenation with sodium without the need for an additional extraction step.
Erfindungsgemäß wird Natrium nicht als Metallsupension, sondern in gelöster Form zur Reaktion eingesetzt. Als Lösungsmittel wird flüssiger Ammoniak verwendet. Aus den physikalischen Eigenschaften von NH3 folgt, daß man flüssigen Ammoniak bei Atmosphärendruck und abgesenkten Temperaturen (Kp = -33,5 °C) oder bei Umgebungstemperatur unter erhöhtem Druck (p = 8 bar bei 20 °C) handhaben kann.According to the invention, sodium is not used as a metal suspension, but in a dissolved form for the reaction. Liquid ammonia is used as the solvent. It follows from the physical properties of NH3 that liquid ammonia can be handled at atmospheric pressure and reduced temperatures (bp = -33.5 ° C) or at ambient temperature under elevated pressure (p = 8 bar at 20 ° C).
Es ist bekannt, daß sich in reinem Ammoniak gelöstes Natrium nur langsam in das schwer lösliche Natriumamid umwandelt, daß diese Umwandlung aber durch verschiedene Katalysatoren, z. B. Eisen-III-Salze, Aktivkohle u. a., stark beschleunigt wird. überraschend wurde gefunden, daß die Dehalogenierung von Halogenwasserstoffen mit Natrium auch in Anwesenheit von solchen Feststoffen, die eine schnelle Abreaktion des Natriums bewirken, glatt verläuft. Das Verfahren kann in unterschiedlichen Ausführungsformen angewandt werden. Nach Variante A wird eine Lösung von Natrium in Ammoniak vorgelegt und der mit Halogenwasserstoff kontaminierte Feststoff unter Rühren zugegeben. In Variante B wird der Feststoff in Ammoniak suspendiert und das matallische Natrium zudosiert. Die Dehalogenierung ist in beiden Varianten nach kurzer Reaktionszeit abgeschlossen. Nahezu vollständiger Umsatz tritt bereits nach einer Minute Kontaktzeit zwischen Natriumlösung und einer wenig porösen Feststoffmatrix ein.It is known that sodium dissolved in pure ammonia converts only slowly into the sparingly soluble sodium amide, but that this conversion is carried out by various catalysts, e.g. B. iron III salts, activated carbon, etc., is greatly accelerated. Surprisingly, it was found that the dehalogenation of hydrogen halides with sodium proceeds smoothly even in the presence of solids which cause the sodium to react rapidly. The method can be used in different embodiments. According to variant A, a solution of sodium in ammonia is presented and the Solid contaminated with hydrogen halide is added with stirring. In variant B, the solid is suspended in ammonia and the metallic sodium is metered in. The dehalogenation is completed in both variants after a short reaction time. Almost complete conversion occurs after just one minute of contact between the sodium solution and a less porous solid matrix.
Für mikroporöse und stark aggregierte Materialien können Kontaktzeiten bis zu 30 Minuten vorteilhaft sein. Längere Reaktionszeiten wirken sich nicht negativ auf das Ergebnis der Umsetzung aus, sie verschlechtern lediglich die Raum-Zeit-Ausbeute. Beide Batch-Varianten sind in analoger Weise für flüssige Abfälle anwendbar. In einer weiteren Ausführungsform (Variante C) wird der kontaminierte Feststoff in einem Festbett angeordnet und von einer Natrium-Lösung in Ammoniak durchströmt. Die Behandlung kann bei Temperaturen nahe dem Siedepunkt von Ammoniak unter Atmosphärendruck oder bei Temperaturen nahe Umgebungstemperatur unter erhöhtem Druck oder unter Bedingungen zwischen diesen Eckpunkten ausgeführt werden.Contact times of up to 30 minutes can be advantageous for microporous and highly aggregated materials. Longer reaction times do not have a negative effect on the result of the reaction, they only worsen the space-time yield. Both batch variants can be used in an analogous manner for liquid waste. In a further embodiment (variant C), the contaminated solid is arranged in a fixed bed and a sodium solution in ammonia flows through it. The treatment can be carried out at temperatures near the boiling point of ammonia under atmospheric pressure or at temperatures near ambient temperature under elevated pressure or under conditions between these corner points.
Alle diese Varianten besitzen aus verfahrenstechnischer Sicht spezifische Vor- und Nachteile, die insbesondere die Reaktorausführung und den Ammoniakkreislauf betreffen. Das Lösungsmittel Ammoniak kann nach beendeter Reaktion entweder als flüssige Phase vom gereinigten Feststoff abgetrennt oder direkt verdampft werden. Die Verdampfung wird in Abhängigkeit von den Reaktionsbedingungen durch Erwärmen und/oder Entspannen erreicht. In jedem Fall wird der Ammoniak im Kreislauf geführt.From a process engineering point of view, all these variants have specific advantages and disadvantages, which relate in particular to the reactor design and the ammonia circuit. The After the reaction has ended, solvent ammonia can either be removed as a liquid phase from the purified solid or evaporated directly. The evaporation is achieved depending on the reaction conditions by heating and / or relaxing. In any case, the ammonia is circulated.
Reaktionstemperaturen oberhalb von 30 °C sind nur dann sinnvoll, wenn dadurch zusätzliche Effekte an der Feststoffmatrix bewirkt werden sollen (z. B. Extraktion von weiteren Schadstoffen). Die Aufarbeitung der Reaktionsprodukte ist von der gewählten Ausführungsform und dem zu reinigenden Abfallprodukt abhängig. Sie enthält folgende Schritte, die in ihrer Reihenfolge unterschiedlich kombiniert werden können: (i) Zersetzung von überschüssigem Natrium durch Zugabe von Wasser oder anderen Reagenzien mit aktivem Wasserstoff (z. B. Methanol, Essigsäure, verdünnte Mineralsäuren o. a.); (ii) Verdampfen des Lösungsmittels durch Erwärmen oder Entspannen, wobei der verdampfte Ammoniak nach erneuter Verflüssigung im Kreislauf zu führen ist; (iii) Waschen und Neutralisieren des gereinigten Feststoffs bzw. der Waschwässer, falls erforderlich. Für eine annähernd vollständige Dehalogenierung ist ein geringer stöchiometrischer Überschuß an Natrium erforderlich, da es durch unerwünschte Nebenreaktionen in unterschiedlichem Umfang verbraucht wird. In der Regel wird dieser Überschuß aus Kostengründen so gering wie möglich gehalten. Unter speziellen Bedingungen kann es auch vorteilhaft sein, mit einem höheren Natriumüberschuß zu arbeiten und vor der Zersetzung eine Phasentrennung festflüssig durchzuführen, um so die noch gebrauchsfähige Natriumlösung für einen weiteren Dehalogenierungsansatz zu nutzen.Reaction temperatures above 30 ° C only make sense if this is to cause additional effects on the solid matrix (e.g. extraction of further pollutants). The processing of the reaction products depends on the chosen embodiment and the waste product to be cleaned. It contains the following steps, which can be combined in different ways: (i) decomposition of excess sodium by adding water or other reagents with active hydrogen (e.g. methanol, acetic acid, dilute mineral acids or the like); (ii) evaporation of the solvent by heating or decompression, the evaporated ammonia being recycled after liquefaction; (iii) washing and neutralizing the cleaned solid or wash water, if necessary. For a nearly complete dehalogenation, a small stoichiometric excess of sodium is required because it is undesirable Side reactions are consumed to different extents. As a rule, this surplus is kept as low as possible for cost reasons. Under special conditions, it can also be advantageous to work with a higher excess of sodium and to carry out a phase separation in solid liquid form before the decomposition in order to use the sodium solution which is still usable for a further dehalogenation batch.
Die Erfindung wird nachfolgend anhand eines typischen Ausführungsbeispiels im Labormaßstab weiter erläutert. Als feste Matrices wurden eine Aktivkohle (Hydraffin 30 der Fa. Lurgi), eine Flugasche aus einem Braunkohlkraftwerk und ein Flußsediment aus der Weißen Elster (lufttrocken) geprüft. Diese Matrices wurden mit folgenden Halogenkohlenwasserstoffen (102 - 104 ppm) beladen: o-Dichlorbenzol, p-Chlorphenol, 1-Chlornaphthalin, 2,3,4-Trichlorbiphenyl, DDT und Lindan. 10 g des dotierten Feststoffs wurden in 30 ml flüssigem Ammoniak suspendiert und einem Magnetrührer unter Atmosphärendruck am Rückfluß (-33 °C) gerührt. In diese Suspension wurden ca. 100 mg metallisches Natrium eingetragen. In der Umgebung des sich schnell auflösenden Natriumstücks trat die charakteristische tiefe Blaufärbung von solvatisiertem Natrium auf.The invention is further explained below on the basis of a typical exemplary embodiment on a laboratory scale. An activated carbon (Hydraffin 30 from Lurgi), a fly ash from a lignite-fired power station and a river sediment from the Weißen Elster (dry air) were tested as solid matrices. These matrices were loaded with the following halogenated hydrocarbons (102-104 ppm): o-dichlorobenzene, p-chlorophenol, 1-chloronaphthalene, 2,3,4-trichlorobiphenyl, DDT and lindane. 10 g of the doped solid were suspended in 30 ml of liquid ammonia and stirred with a magnetic stirrer under atmospheric pressure at reflux (-33 ° C.). About 100 mg of metallic sodium were introduced into this suspension. The characteristic deep blue coloration of solvated sodium occurred in the vicinity of the rapidly dissolving piece of sodium.
Unmittelbar nach dem vollständigen Auflösen des Natriums wurde der Rückflußkühler entfernt und der Ammoniak innerhalb weniger Minuten abgedampft. Der feste Rückstand wurde mit verdünnter Säure gequencht und mit verschiedenen organischen Lösungsmitteln extrahiert. Die Extrakte wurden gaschromatographisch analysiert (FID und ECD als Detektoren). In der wäßrigen Phase wurde durch Ionenchromatographie die Konzentration an Chloridionen bestimmt.Immediately after the sodium had completely dissolved, the reflux condenser was removed and the ammonia inside evaporated less minutes. The solid residue was quenched with dilute acid and extracted with various organic solvents. The extracts were analyzed by gas chromatography (FID and ECD as detectors). The concentration of chloride ions in the aqueous phase was determined by ion chromatography.
Als Ergebnis der Chloridanalyse wurde das mit dem Feststoff zugeführte Organochlor vollständig als Chlorid wiedergefunden (98 + 3 %). Die Analyse der organischen Extrakte wies Umsätze der Chlorkohlenwasserstoffe zwischen 95 und >99 % aus. Als Hauptprodukte wurden die erwarteten Dechlorierungsprodukte Benzol, Phenol, Naphtalin, Biphenyl und Methylfluoren neben geringen Mengen partiell hydrierter Kohlenwasserstoffe (z. B. Dihydronapthaline) nachgewiesen.As a result of the chloride analysis, the organochlor added with the solid was completely recovered as chloride (98 + 3%). The analysis of the organic extracts showed sales of chlorinated hydrocarbons between 95 and> 99%. The main products were the expected dechlorination products benzene, phenol, naphthalene, biphenyl and methyl fluorene in addition to small amounts of partially hydrogenated hydrocarbons (e.g. dihydronapthalenes).
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4324931A DE4324931A1 (en) | 1993-07-24 | 1993-07-24 | Process for the reductive dehalogenation of solid and liquid substances containing organohalogen |
DE4324931 | 1993-07-24 |
Publications (2)
Publication Number | Publication Date |
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EP0635283A1 true EP0635283A1 (en) | 1995-01-25 |
EP0635283B1 EP0635283B1 (en) | 1999-01-20 |
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ID=6493654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94250184A Revoked EP0635283B1 (en) | 1993-07-24 | 1994-07-20 | Process for the reductive dehalogenation of solid materials containing organohalogens |
Country Status (3)
Country | Link |
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EP (1) | EP0635283B1 (en) |
AT (1) | ATE175882T1 (en) |
DE (2) | DE4324931A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0880378A1 (en) * | 1995-11-07 | 1998-12-02 | Commodore Applied Technologies, Inc. | Method and apparatus to destroy chemical warfare agents |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2003230638A (en) * | 2002-02-07 | 2003-08-19 | Toshiba Corp | System for detoxifying harmful organochlorine compound and method for recycling product and waste produced by the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2017143A (en) * | 1978-03-25 | 1979-10-03 | Degussa | Process for regenerating spent lubricating oils |
EP0288408A1 (en) * | 1987-03-30 | 1988-10-26 | A.L. Sandpiper Corporation | Processes for decontaminating polluted substrates |
US4910353A (en) * | 1983-02-07 | 1990-03-20 | Transformer Service, Inc. | Dehalogenation of polychlorinated biphenyls and other related compounds |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2249679C3 (en) * | 1972-10-11 | 1980-09-11 | Bayer Ag, 5090 Leverkusen | Process for the preparation of 9cis Tricosen, Muscalure |
CH668709A5 (en) * | 1985-12-06 | 1989-01-31 | Ciba Geigy Ag | METHOD FOR ENTHALOGENATING POLYHALOGENATED ALIPHATIC AND AROMATIC COMPOUNDS. |
-
1993
- 1993-07-24 DE DE4324931A patent/DE4324931A1/en not_active Withdrawn
-
1994
- 1994-07-20 DE DE59407681T patent/DE59407681D1/en not_active Expired - Fee Related
- 1994-07-20 EP EP94250184A patent/EP0635283B1/en not_active Revoked
- 1994-07-20 AT AT94250184T patent/ATE175882T1/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2017143A (en) * | 1978-03-25 | 1979-10-03 | Degussa | Process for regenerating spent lubricating oils |
US4910353A (en) * | 1983-02-07 | 1990-03-20 | Transformer Service, Inc. | Dehalogenation of polychlorinated biphenyls and other related compounds |
EP0288408A1 (en) * | 1987-03-30 | 1988-10-26 | A.L. Sandpiper Corporation | Processes for decontaminating polluted substrates |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 76, no. 13, 27 March 1972, Columbus, Ohio, US; abstract no. 69170s, M.V.KENNEDY ET AL: "Chemical and Thermal Aspects of Pesticide Disposal" page 115; column 2; * |
CHEMICAL ABSTRACTS, vol. 83, no. 14, 6 October 1975, Columbus, Ohio, US; abstract no. 125874h, E.S.LAHANIATAS ET AL: "Ecological chemistry. XCIV. Analysis and photochemistry of high-boiling polychlorinated paraffin mixtures" page 805; column 1; * |
J.DE LANNOY ET AL: "Sodium-Ammonia Reductions in N-Heteroaromatic Chemistry.", BULLETIN DES SOCIETES CHIMIQUES BELGES, vol. 79, 1970, OXFORD GB, pages 329 - 336 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0880378A1 (en) * | 1995-11-07 | 1998-12-02 | Commodore Applied Technologies, Inc. | Method and apparatus to destroy chemical warfare agents |
EP0880378A4 (en) * | 1995-11-07 | 1999-03-24 | Commodore Applied Technologies | Method and apparatus to destroy chemical warfare agents |
US5998691A (en) * | 1995-11-07 | 1999-12-07 | Commodore Applied Technologies, Inc. | Method and apparatus to destroy chemical warfare agents |
Also Published As
Publication number | Publication date |
---|---|
EP0635283B1 (en) | 1999-01-20 |
ATE175882T1 (en) | 1999-02-15 |
DE4324931A1 (en) | 1995-01-26 |
DE59407681D1 (en) | 1999-03-04 |
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