EP0184342B1 - Destroying halogen containing organic compounds - Google Patents
Destroying halogen containing organic compounds Download PDFInfo
- Publication number
- EP0184342B1 EP0184342B1 EP85308218A EP85308218A EP0184342B1 EP 0184342 B1 EP0184342 B1 EP 0184342B1 EP 85308218 A EP85308218 A EP 85308218A EP 85308218 A EP85308218 A EP 85308218A EP 0184342 B1 EP0184342 B1 EP 0184342B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- compounds
- destroyed
- aluminium
- containing organic
- 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.)
- Expired
Links
Classifications
-
- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
Definitions
- PCB's Polychlorinated biphenyls
- PCB's are non- conductors of electricity and have good resistance to high temperatures, so they are widely used as working fluids in heat exchangers and hydraulic systems and by the electrical industry in transformers and capacitors.
- PCB's are extremely toxic, but are difficult to destroy on account of their thermal stability and chemical inertness.
- the standard destruction method involves incineration at temperatures around 1500°C, but suffers from several disadvantages. Operation at these very high temperatures is expensive; and incomplete combustion can give rise to chlorinated dioxins or furans which are even more toxic than PCB's.
- the present invention provides a method for the destruction of PCB's and related compounds which involves reaction with metal rather than combustion, and operates at much lower temperatures.
- Shultz discloses as a non preferred embodiment, but does not claim, a process which involves contacting PCB's with a solid aluminium surface.
- his experiments involved heating transformer oils containing PCB's in the presence of aluminium foil at various temperatures, but did not result in complete destruction of the PCB's even over periods as long as 30 minutes.
- Japanese Kokai 51-25471 describes a method of decomposing PCB's by heating them to effect partial dissociation to HCI OR CI 2 , and passing the mixture over a suitable metal and recovering a chloride salt of the metal by sublimation from the decomposition system. There is no indication that air is excluded; and no evidence that complete decomposition of PCB's is achieved even after several hours reaction.
- the invention is based on the discovery that PCB's can be rapidly destroyed by heating in the presence of solid aluminium, but only provided certain critical parameters are observed.
- the invention thus provides a method of destroying halogen-containing organic compounds by reaction with a metal in the solid state at elevated temperature, characterized by contacting the compounds in gaseous form in the absence of oxygen with a metal selected from AI, Mg, Si, Ti and Be, an alloys thereof having a specific surface area in the range of from 0.1 to 65 m 2 of active metal surface per gram of compound to be destroyed and at a temperature of at least 450°C and for a contact time of up to 50 seconds, whereby the halogen-containing organic compounds are destroyed and a deactivating carbonaceous deposit is formed on the surface of the metal.
- the compounds are preferably entrained in an inert carrier gas, for example argon or other gas in group 0 of the periodic table.
- an inert carrier gas for example argon or other gas in group 0 of the periodic table.
- High purity nitrogen may also be used, and is regarded for this purpose as an inert gas.
- nitrogen is known to form highly toxic compounds with PCB's but the concetra- tions so far observed of these are insignificant.
- concentration of the compounds in carrier gas is preferably from 10 ppm up to 10%.
- metals that can be used for reaction with the compounds are specified Al, Mg, Si, Ti and Be, and alloys of these metals with each other or with minor proportions of other metals.
- the five named metals have two characteristics in common: they form oxides having electically insulating properties; and the oxides have high thermal and chemical stability.
- Berylium presents a toxicity problem in itself, and is on that account the least preferred.
- the most preferred metals are magensium and, particularly, aluminium.
- the metals can be used in the natural state, i.e. without the need to remove any oxide film that may be present.
- Aluminium can be used having an anodic oxide film which may contain minor proportions of oxides of other metals such as Co, Ni, Sn, Cu etc., in the pores. It is not known with certainty whether any oxide film remains during operation of the method, or whether it is removed by reaction with halogen-containing organic compounds.
- the metal can be used in any physical form in which is has a high specific surface area. Suitable forms include a packed bed of spheres, chips or granules, a fluidized bed of powder, honeycomb, wire mesh or wire wool. Our presently preferred material is scrap aluminium and alloys thereof in granulated form, because this is cheap and readily obtainable. Sufficient metal surface area should be provided to ensure rapid and complete destruction of the halogen-containing organic compounds. This is generally 0.1 to 65 m 2 , preferably from 1 to 20 m 2 , of active metal surface (not necessarily bare metal surface, but surface not coated with e.g. inactivating carbonaceous deposits) per gram, of compound to be destroyed.
- reaction temperature needs to be at least 450°C.
- An upper limit on temperature is set by the melting point of the metal being used.
- One of the advantages of the method of this invention is the low temperature required, and it is preferred not to use higher temperatures than are necessary in orderto achieve reaction at the desired rate. Depending on other conditions, preferred reaction temperatures are likely to lie in the range 550°C to 650°C.
- Reaction products resulting from the method appear to be metal halide (e.g. aluminium chloride), low-boiling hydrocarbons, halogen, (e.g. chlorine) and carbon deposited on the metal substrate.
- metal halide e.g. aluminium chloride
- low-boiling hydrocarbons e.g. carbon
- halogen e.g. chlorine
- carbon deposited on the metal substrate As a result of this deposition, the substrate gradually becomes inactive. When this happens, the substrate can be regenerated. With aluminium, this can be achieved by subjecting the metal to sodium hydroxide solution, or less preferably, by heating the metal in air to burn off the carbon deposits.
- Other treatments for regenerating aluminium involve exposing the carbonised surface:
- Hydrogen and chlorine may be diluted with flowing argon.
- treatment (a) is preferred. It seems possible that the regenerated surface is in some way "re-activated" by the chlorine. Using this treatment, a 79.7% recovery of usable surface was obtained.
- Treatment (b) is more preferred than (c).
- Other metal substrates can similarly be regenerated by removing the carbon deposits under conditions in which the substrate is not effected.
- the metal used was 1100 aluminium alloy chips (0.5 x 0.5 x 0.1 cm). A bed about 27 cm long of these chips was positioned in a vertical quartz tube 1.8 cm outside diameter, and maintained at a nominal temperature of 580°C. A vessel containing the reactant was positioned in the quartz tube below the bed, and was surrounded by a separate tube furnace whose temperature was raised from ambient to 600°C over a period of 60 minutes. The lower end of the quartz tube was closed except for an inlet port through which argon carrier gas was passed at a flow rate of 87.7 ml/min (NTP). As the reactant heated up it vapourized and became entrained in the carrier gas.
- NTP argon carrier gas
- the flow rate was such that the residence time of the gas in the bed of aluminium chips was about 15 seconds.
- the temperature profile of the bed of chips was measured as 366°C at 0 cm up from the bottom; 473°C at 5 cm; 563°C at 9 cm; 601°C at 16 cm and 600°C at 27 cm.
- the top end of the quartz tube was closed except for a gas outlet, and the reaction products were condensed. After the experiment, any remaining reactant, the material in the bed of aluminium chips and the reaction products were all analysed for halogen-containing organic compounds.
- the reactant was 0.0078 g of decachlorobiphenyl.
- the destruction efficiency was 99.9999%.
- the section from 14 to 24 cm (measured from the bottom) of the aluminium bed became black.
- the rate of heating of the reactant sample was varied so that the concentration of decachlorobiphenyl in carrier argon gas ranged from 166 ppm to 3048 ppm. In all cases, the destruction efficiency was at least 99.999%.
Abstract
Description
- Polychlorinated biphenyls (PCB's) is a generic term covering a family of partially or wholly chlorinated isomers or biphenyl. PCB's are non- conductors of electricity and have good resistance to high temperatures, so they are widely used as working fluids in heat exchangers and hydraulic systems and by the electrical industry in transformers and capacitors. PCB's are extremely toxic, but are difficult to destroy on account of their thermal stability and chemical inertness. The standard destruction method involves incineration at temperatures around 1500°C, but suffers from several disadvantages. Operation at these very high temperatures is expensive; and incomplete combustion can give rise to chlorinated dioxins or furans which are even more toxic than PCB's. The present invention provides a method for the destruction of PCB's and related compounds which involves reaction with metal rather than combustion, and operates at much lower temperatures.
- C. S. Shultz describes in U.S. Patent 4,469,661 a method for destroying PCB's by contacting them in vapour form with molten aluminium metal. This process, which is not demonstrated by Shultz, is unsatisfactory for several reasons. The use of a body of molten aluminium metal is somewhat hazardous, on account of the risk of explosion, and expensive, on account of the high temperatures involved (aluminium melts at 660°C) and the difficulty of containing molten aluminium which aggressively attacks standard materials such as steel and quartz. It is expected to be more difficult to ensure intimate physical contact of gaseous PCB's with molten aluminium than with aluminium in the solid state; and that the reaction of PCB's with molten aluminium will produce much more AIC13 than will reaction with aluminium in the solid state.
- Shultz discloses as a non preferred embodiment, but does not claim, a process which involves contacting PCB's with a solid aluminium surface. As reported in Examples 1 to 3, his experiments involved heating transformer oils containing PCB's in the presence of aluminium foil at various temperatures, but did not result in complete destruction of the PCB's even over periods as long as 30 minutes.
- Japanese Kokai 51-25471 describes a method of decomposing PCB's by heating them to effect partial dissociation to HCI OR CI2, and passing the mixture over a suitable metal and recovering a chloride salt of the metal by sublimation from the decomposition system. There is no indication that air is excluded; and no evidence that complete decomposition of PCB's is achieved even after several hours reaction.
- This invention is based on the discovery that PCB's can be rapidly destroyed by heating in the presence of solid aluminium, but only provided certain critical parameters are observed. The invention thus provides a method of destroying halogen-containing organic compounds by reaction with a metal in the solid state at elevated temperature, characterized by contacting the compounds in gaseous form in the absence of oxygen with a metal selected from AI, Mg, Si, Ti and Be, an alloys thereof having a specific surface area in the range of from 0.1 to 65 m2 of active metal surface per gram of compound to be destroyed and at a temperature of at least 450°C and for a contact time of up to 50 seconds, whereby the halogen-containing organic compounds are destroyed and a deactivating carbonaceous deposit is formed on the surface of the metal.
- Tests have established that the method is capable of destroying a wide range of chlorinated organic compounds. We know of no reason why any chlorinated organic compound, hwich is thermally stable enough to be heated up to the required reaction temperature, should not be destroyed by the method. The invention is also applicable to organic compounds of the other halogens, fluorine, bromine and iodine. However, environmental problems do not exist to the same extent as with chlorine compounds because of the far greater industrial use of the latter. The invention is, of course, of particular value in relation to PCB's and related compounds.
- It is necessary that the compounds should be in the gas phase, for reaction of liquid compounds with solid metal has not proved effective. The compounds are preferably entrained in an inert carrier gas, for example argon or other gas in group 0 of the periodic table. High purity nitrogen may also be used, and is regarded for this purpose as an inert gas. However, its use is not preferred, for nitrogen is known to form highly toxic compounds with PCB's but the concetra- tions so far observed of these are insignificant.
- There is no critical upper limit of concentration of the compounds in carrier gas. The method works without a carrier gas, provided that sufficient metal surface area is available for reaction, but would only be safe with a completely closed reaction vessel. In industrial practice, safety considerations determine an upper limit of concentration. There is no critical lower limit of concentration, but a practical lower limit is generally determined by economic factors. The concentration of halogen-containing organic compounds in carrier gas is preferably from 10 ppm up to 10%.
- It is at all events necessary that oxygen, and compounds that might generate oxygen in situ, be substantially absent. If the method is performed in the presence of significant quantities of oxygen, then destruction of PCB's is incomplete and there is the risk of formation of chlorinated dioxins of furans.
- As metals that can be used for reaction with the compounds, are specified Al, Mg, Si, Ti and Be, and alloys of these metals with each other or with minor proportions of other metals. The five named metals have two characteristics in common: they form oxides having electically insulating properties; and the oxides have high thermal and chemical stability. Berylium presents a toxicity problem in itself, and is on that account the least preferred. The most preferred metals are magensium and, particularly, aluminium. The metals can be used in the natural state, i.e. without the need to remove any oxide film that may be present. Aluminium can be used having an anodic oxide film which may contain minor proportions of oxides of other metals such as Co, Ni, Sn, Cu etc., in the pores. It is not known with certainty whether any oxide film remains during operation of the method, or whether it is removed by reaction with halogen-containing organic compounds.
- The metal can be used in any physical form in which is has a high specific surface area. Suitable forms include a packed bed of spheres, chips or granules, a fluidized bed of powder, honeycomb, wire mesh or wire wool. Our presently preferred material is scrap aluminium and alloys thereof in granulated form, because this is cheap and readily obtainable. Sufficient metal surface area should be provided to ensure rapid and complete destruction of the halogen-containing organic compounds. This is generally 0.1 to 65 m2, preferably from 1 to 20 m2, of active metal surface (not necessarily bare metal surface, but surface not coated with e.g. inactivating carbonaceous deposits) per gram, of compound to be destroyed.
- To achieve sufficiently rapid reaction, the reaction temperature needs to be at least 450°C. An upper limit on temperature is set by the melting point of the metal being used. One of the advantages of the method of this invention is the low temperature required, and it is preferred not to use higher temperatures than are necessary in orderto achieve reaction at the desired rate. Depending on other conditions, preferred reaction temperatures are likely to lie in the range 550°C to 650°C.
- Provided the above reaction conditions: absence of oxygen; state of metal; temperature of the metal, are maintained as described above, destruction of halogen-containing organic compounds are achieved at short contact times. We specify a range of up to 50 seconds, typically from 0.1 to 50 seconds, more typically from 0.5 to 50 seconds and preferably 0.5 to 30 seconds contact time. In a continuous system, this is the average residence time of gas in the region of the active metal surface. Clearly reaction time is related to the total surface area of metal per unit of halogen-containing organic compounds, and to the reaction tempeature. Adjustment of gas flow to ensure complete destruction of the compounds is achieved by routine trial and error.
- Reaction products resulting from the method appear to be metal halide (e.g. aluminium chloride), low-boiling hydrocarbons, halogen, (e.g. chlorine) and carbon deposited on the metal substrate. As a result of this deposition, the substrate gradually becomes inactive. When this happens, the substrate can be regenerated. With aluminium, this can be achieved by subjecting the metal to sodium hydroxide solution, or less preferably, by heating the metal in air to burn off the carbon deposits. Other treatments for regenerating aluminium involve exposing the carbonised surface:
- (a) at 580°C to oxygen for 20 minutes followed by chlorine for 1 minute.
- (b) hydrogen for 30 minutes at 550°C followed by oxygen for 30 minutes.
- (c) oxygen for 30 minutes at 550-580°C followed by a steam/oxygen mixture at 125-175°C.
- Hydrogen and chlorine may be diluted with flowing argon. Of the above, treatment (a) is preferred. It seems possible that the regenerated surface is in some way "re-activated" by the chlorine. Using this treatment, a 79.7% recovery of usable surface was obtained. Treatment (b) is more preferred than (c). Other metal substrates can similarly be regenerated by removing the carbon deposits under conditions in which the substrate is not effected.
- The following examples illustrate the invention.
- The metal used was 1100 aluminium alloy chips (0.5 x 0.5 x 0.1 cm). A bed about 27 cm long of these chips was positioned in a vertical quartz tube 1.8 cm outside diameter, and maintained at a nominal temperature of 580°C. A vessel containing the reactant was positioned in the quartz tube below the bed, and was surrounded by a separate tube furnace whose temperature was raised from ambient to 600°C over a period of 60 minutes. The lower end of the quartz tube was closed except for an inlet port through which argon carrier gas was passed at a flow rate of 87.7 ml/min (NTP). As the reactant heated up it vapourized and became entrained in the carrier gas. The flow rate was such that the residence time of the gas in the bed of aluminium chips was about 15 seconds. The temperature profile of the bed of chips was measured as 366°C at 0 cm up from the bottom; 473°C at 5 cm; 563°C at 9 cm; 601°C at 16 cm and 600°C at 27 cm. The top end of the quartz tube was closed except for a gas outlet, and the reaction products were condensed. After the experiment, any remaining reactant, the material in the bed of aluminium chips and the reaction products were all analysed for halogen-containing organic compounds.
- In one experiment, the reactant was 0.0078 g of decachlorobiphenyl. The destruction efficiency was 99.9999%. The section from 14 to 24 cm (measured from the bottom) of the aluminium bed became black.
- In other experiments, the rate of heating of the reactant sample was varied so that the concentration of decachlorobiphenyl in carrier argon gas ranged from 166 ppm to 3048 ppm. In all cases, the destruction efficiency was at least 99.999%.
- After one experiment, dry air is passed through the bed of aluminium chips at 580°C. The bed, a section of which had been blackened by carbon deposition, was partially regenerated by contact with air. Only very little black colour remained on the aluminium surface.
- Comparative experiments were run under the same conditions but with an empty bed, i.e. without the aluminium chips. Destruction efficiency was of the order of 0 to 5%. This demonstrates the excellent high temperature stability of decachlorobiphenyl under normal circumstances, and the dramatic effect produced by the bed of aluminium chips.
- Other halogen-containing organic compound reactants were destroyed by the laboratory method described in Example 1. Destruction efficiency was not measured with the same accuracy as in Example 1, because of the lack of analytical techniques for measuring small amounts of different halogenated organic compounds.
- a) The reactant was 0.5 ml of carbontetra- chloride, injected at ambient temperature into the carrier gas. The bed of aluminium chips was one that had been regenerated by air as described in Example 1. The destruction efficiency was not measured accurately, but was high.
- b) The reactant was 0.2 ml of ethylene dich= loride, injected at ambient temperature into the carrier gas. The destruction efficiency was greater than 90%.
- c) The reactant was 1.0 ml of Freon-113, injected into the carrier gas. The destruction efficiency was greater than 90%
- d) The reactant was 0.0052 g of "Vitar" fluorocarbon. This was all decomposed in the sample vial and did not reach the bed of aluminium chips.
- e) The reactant was 0.0613 g of iodobenzene. The destruction efficiency was 99.6%.
- f) The reactant was 0.0185 g of pyranol transformer oil containing 60% by weight of penta- chlorobiphenyl. The concentration of reactant in the argon carrier gas was 1000 to 2000 ppm. The destruction efficiency was 98%.
- This example demonstrates the use of different metal substrates in the laboratory method generally described in Example 1.
- a) A bed of aluminium alloy chips was used (as described in Example 1). The bed had been previously used and had been regenerated by treatment with an aqueous solution containing about 5 g of sodium hydroxide per litre which was effective to remove all the carbon residues. The reactant was 0.0261 g of pentachlorophenol. The destruction efficiency was greater than 95%.
- b) The bed comprised anodized aluminium chips made from a sheet of 5352 alloy with a 7.5 micron anodic oxide film which had been coloured electrically with cobalt. The size of the chips was 0.5 x 0.5 x 0.1 cm. Both sides of the chips were coloured black with cobalt but the periphery was bare 5252 alloy. The reactant was 0.0049 g of decachlorobiphenyl. The destruction efficiency was 99.999%.
- c) The bed was composed of aluminium fines, that is to say particles which passed through a 20 mesh sieve (opening 0.84 mm). The reactant was 0.06 g of pyranol transformer oil. The destruction efficiency was 99.99%.
- d) The bed was of 70 to 80 mesh (about 0.2 mm opening) magnesium metal powder. The reactant was 0.009 g of decachlorobiphenyl. The destruction efficiency was 99.999%.
- This example demonstrates how the carrier gas can be altered or omitted. Where not otherwise stated, conditions were as described above in Example 1.
- a) The bed was of super pure aluminium fines of a particle size to pass through a 20 mesh sieve (opening 0.84 mm). The reactant was about 0.0078 g of decachlorobiphenyl. No carrier gas was used. The reactant was heated from ambient temperature to 580°C in 15 minutes and maintained at 580°C for a further 15 minutes. The destruction efficiency was 99.999%. The amount of aluminium used was 146 grams per gram of decachioro-jjipheny), but further experiments demonstrated that less than 100 grams per gram were equally effective. While it is not meaningful to talk about a contact time between reactant and substrate in a laboratory experiment of this kind, in commercial operation there would always be a flow of gas over the substrate bed.
- b) The bed was of aluminium alloy chips as used in Example 1. Instead of argon, pre-purified nitrogen was used as the carrier gas at a flow rate of 87.7 ml/min (NTP). The reactant was 0.0065 g of decachlorobiphenyl, and the destruction efficiency was 99.999%.
- In a comparative experiment, extra dry air was used as the carrier gas in place of nitrogen. The destruction efficiency was less than 80%, and unidentified and possibly toxic produces were found in the effluent gas.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85308218T ATE40528T1 (en) | 1984-11-23 | 1985-11-12 | DESTRUCTION OF HALOGEN-CONTAINING ORGANIC COMPOUNDS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8429709 | 1984-11-23 | ||
GB848429709A GB8429709D0 (en) | 1984-11-23 | 1984-11-23 | Halogen-containing organic compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0184342A1 EP0184342A1 (en) | 1986-06-11 |
EP0184342B1 true EP0184342B1 (en) | 1989-02-01 |
Family
ID=10570205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85308218A Expired EP0184342B1 (en) | 1984-11-23 | 1985-11-12 | Destroying halogen containing organic compounds |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0184342B1 (en) |
JP (1) | JPS61137831A (en) |
AT (1) | ATE40528T1 (en) |
AU (1) | AU586840B2 (en) |
BR (1) | BR8505887A (en) |
CA (1) | CA1258682A (en) |
DE (1) | DE3568009D1 (en) |
ES (1) | ES8704867A1 (en) |
GB (1) | GB8429709D0 (en) |
IN (1) | IN165170B (en) |
NO (1) | NO163265C (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5276250A (en) * | 1986-07-11 | 1994-01-04 | Hagenmaier Hans Paul | Process for decomposing polyhalogenated compounds |
DE3623492A1 (en) * | 1986-07-11 | 1988-01-21 | Hagenmaier Hans Paul | METHOD FOR DEGRADING HALOGENATED AROMATES |
GB8813270D0 (en) * | 1988-06-04 | 1988-07-06 | Plasma Products Ltd | Dry exhaust gas conditioning |
DE3820317A1 (en) * | 1988-06-15 | 1989-12-21 | Christian O Schoen | Process for separating flowable organic media containing harmful or polluting constituents |
DE3932927A1 (en) * | 1989-10-03 | 1991-04-18 | Hansjoerg Prof Dr Sinn | Dehalogenating organo-halogen-contg. hydrocarbon - by passing vaporous educts through with sodium-vapour pressure corresp. to temp. and measuring residence time |
US5141629A (en) * | 1990-05-15 | 1992-08-25 | State Of Israel, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
ATE250443T1 (en) * | 1998-02-10 | 2003-10-15 | Miyoshi Yushi Kk | METHOD FOR TREATING SOLID WASTE |
JP4954133B2 (en) * | 2008-03-31 | 2012-06-13 | 本田技研工業株式会社 | Oil passage structure |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2346562A (en) * | 1940-11-07 | 1944-04-11 | Dow Chemical Co | Method of removing carbonized oil residue from magnesium articles |
FR1190669A (en) * | 1957-12-03 | 1959-10-14 | Pechiney | Manufacture of organic aluminum derivatives |
US2977323A (en) * | 1958-07-14 | 1961-03-28 | Phillips Petroleum Co | Process for reactivating used cracking catalysts |
US3343911A (en) * | 1964-02-20 | 1967-09-26 | Pittsburgh Plate Glass Co | Production of aluminum trichloride |
US3481877A (en) * | 1967-02-27 | 1969-12-02 | Amchem Prod | Cleaning solution concentrate and method of preparing same |
JPS5125471A (en) * | 1974-08-28 | 1976-03-02 | Arita Kenkyusho Kk | Horienkabifueniiru no bunkaiho |
JPS5729313A (en) * | 1980-07-28 | 1982-02-17 | Hideo Koga | Suprort for bedding |
US4469661A (en) * | 1982-04-06 | 1984-09-04 | Shultz Clifford G | Destruction of polychlorinated biphenyls and other hazardous halogenated hydrocarbons |
US4447262A (en) * | 1983-05-16 | 1984-05-08 | Rockwell International Corporation | Destruction of halogen-containing materials |
-
1984
- 1984-11-23 GB GB848429709A patent/GB8429709D0/en active Pending
-
1985
- 1985-11-12 EP EP85308218A patent/EP0184342B1/en not_active Expired
- 1985-11-12 AT AT85308218T patent/ATE40528T1/en not_active IP Right Cessation
- 1985-11-12 DE DE8585308218T patent/DE3568009D1/en not_active Expired
- 1985-11-21 CA CA000495858A patent/CA1258682A/en not_active Expired
- 1985-11-22 AU AU50353/85A patent/AU586840B2/en not_active Ceased
- 1985-11-22 NO NO854693A patent/NO163265C/en unknown
- 1985-11-22 IN IN984/DEL/85A patent/IN165170B/en unknown
- 1985-11-22 JP JP60263640A patent/JPS61137831A/en active Pending
- 1985-11-22 ES ES549182A patent/ES8704867A1/en not_active Expired
- 1985-11-22 BR BR8505887A patent/BR8505887A/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE3568009D1 (en) | 1989-03-09 |
JPS61137831A (en) | 1986-06-25 |
NO163265C (en) | 1990-05-02 |
NO854693L (en) | 1986-05-26 |
AU5035385A (en) | 1986-05-29 |
ATE40528T1 (en) | 1989-02-15 |
ES8704867A1 (en) | 1987-04-16 |
GB8429709D0 (en) | 1985-01-03 |
CA1258682A (en) | 1989-08-22 |
ES549182A0 (en) | 1987-04-16 |
IN165170B (en) | 1989-08-19 |
BR8505887A (en) | 1986-08-12 |
EP0184342A1 (en) | 1986-06-11 |
NO163265B (en) | 1990-01-22 |
AU586840B2 (en) | 1989-07-27 |
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