DK166432B1 - PROCEDURE FOR DEGREE OF ORGANIC CHLORED COMPOUNDS - Google Patents
PROCEDURE FOR DEGREE OF ORGANIC CHLORED COMPOUNDS Download PDFInfo
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- DK166432B1 DK166432B1 DK023288A DK23288A DK166432B1 DK 166432 B1 DK166432 B1 DK 166432B1 DK 023288 A DK023288 A DK 023288A DK 23288 A DK23288 A DK 23288A DK 166432 B1 DK166432 B1 DK 166432B1
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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
- A62D3/32—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or metals
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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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract
Description
Den foreliggende opfindelse angår en fremgangsmåde til nedbrydning af organiske chlorerede forbindelser, især aromatiske forbindelser og polychlorbiphenyler.The present invention relates to a process for the degradation of organic chlorinated compounds, especially aromatic compounds and polychlorobiphenyls.
DK 166432 B1 i 5 Visse af de elektriske væsker indeholder chlorerede organiske forbindelser og efter en vis tids anvendelse nedbrydes de, og bør udskiftes. Man kan undertiden regenerere væskerne totalt eller partielt, men man er ofte nødt til at destruere en del af disse væsker.Some of the electrical fluids contain chlorinated organic compounds and after a certain period of use they decompose and should be replaced. You can sometimes regenerate the liquids completely or partially, but you often have to destroy some of these liquids.
1010
Chlorerede organiske produkter, såvel som visse pesticider, chlorerede aromatiske forbindelser såsom hexachlor-benzen eller polychlorbiphenyler (PCB) kan danne toxiske forbindelser, når de forbrændes som et almindeligt, 15 brændbart produkt.Chlorinated organic products, as well as certain pesticides, chlorinated aromatic compounds such as hexachlorobenzene or polychlorobiphenyls (PCBs) can form toxic compounds when incinerated as a common combustible product.
For at undgå at danne toxiske forbindelser destruerer man disse chlorerede forbindelser ved høj temperatur og under specifikke omstændigheder.To avoid the formation of toxic compounds, these chlorinated compounds are destroyed at high temperature and under specific conditions.
20 I en artikel SCI. TOTAL ENVIRON. 1978, 10 (1) 51-9, omtales destruktionen af polychlorbiphenyler (PCB) ved afbrænding med en opholdstid længere end 2 sekunder.20 In an article SCI. TOTAL ENVIRON. 1978, 10 (1) 51-9, discloses the destruction of polychlorinated biphenyls (PCBs) by burning with a residence time longer than 2 seconds.
25 I en anden artikel PROC. ANNU. MEET - AIR POLLUT. CONTROL ASSOC. 1977 (Bind 2) indlæg Nr. 33, omtales en destruktion med et omfang på 99,9995% af PCB ved 1000 °C med en opholdstid på 2 sekunder.25 In another article PROC. Annu. MEET - AIR POLLUT. CONTROL ASSOC. 1977 (Volume 2) entry no. 33, a destruction of 99.9995% of PCB is mentioned at 1000 ° C with a residence time of 2 seconds.
30 I europæisk patentskrift nr. EP 170714 omtales destruktionen af PCB ved reaktion med smeltet aluminium eller med et aluminiumbaseret eutektikum, idet reaktionen finder sted ved temperaturer over 382 °C. 1European Patent Application EP 170714 discloses the destruction of PCBs by reaction with molten aluminum or with an aluminum-based eutectic, the reaction taking place at temperatures above 382 ° C. 1
Problemet ved disse fremgangsmåder er, at man skal destruere ved meget høje temperaturer, dvs. temperaturer over 300 °C.The problem with these methods is that they have to be destroyed at very high temperatures, ie. temperatures above 300 ° C.
2 DK 166432 B1 I Chemical Abstracts, bind 87 (1977) nr. 188873k refereres til artiklen NIPPON KAGAKUKAISHI 1977 (9) P. 1407 til 1409, 5 hvor der omtales en metode til destruering af polychlore-rede biphenyler ved temperaturer under 300 °C. De poly-chlorerede biphenyler (PCB) destrueres ved, at de bringes i kontakt med en smeltet blanding af AlClg, NaCl og KC1, 10 samt evt. aluminiumspulver. Det fremgår af artiklen at koncentrationer af PCB i chloraluminatet før reaktionen er mellem 10000 og 20000 ppm.2 DK 166432 B1 In Chemical Abstracts, Volume 87 (1977) No. 188873k, reference is made to article NIPPON KAGAKUKAISHI 1977 (9) P. 1407 to 1409, 5 which discloses a method for destroying polychlorinated biphenyls at temperatures below 300 ° C. . The polychlorinated biphenyls (PCBs) are destroyed by contacting them with a molten mixture of AlClg, NaCl and KCl, as well as any. aluminum powder. It appears from the article that concentrations of PCB in the chloro aluminate prior to the reaction are between 10000 and 20000 ppm.
Den ovenfor beskrevne metode er dog ikke blevet anvendt 15 særligt meget, idet det ved hjælp af de i artiklen angivne anvisninger ikke har været muligt at opnå en dekompo-neringseffekt på mere end ca. 70%.However, the above-described method has not been used very much, since it has not been possible to achieve a decomposition effect of more than approx. 70%.
Formålet med den foreliggende opfindelse er at anvise en 20 fremgangsmåde til nedbrydning af organisk chlorerede forbindelser omfattende mere end to carbonatomer, hvilken fremgangsmåde kan forløbe ved temperaturer under 300 °C og ved hjælp af hvilken fremgangsmåde man kan opnå en høj nedbrydningseffekt.The object of the present invention is to provide a process for the decomposition of organic chlorinated compounds comprising more than two carbon atoms, which process can proceed at temperatures below 300 ° C and by means of which a high decomposition effect can be obtained.
2525
Fremgangsmåden ifølge opfindelsen, der er af den i krav l's indledning angivne art, er ejendommelig ved det i den kendetegnende del af krav 1 angivne.The method according to the invention, which is of the kind set out in the preamble of claim 1, is characterized by the method of claim 1.
30 Ved denne fremgangsmåde opnås en væsentlig højere nedbrydningseffekt på en kortere tid end ved den ovennævnte kendte metode.In this method, a significantly higher degradation effect is obtained in a shorter time than by the aforementioned known method.
Man kan anvende forskellige metalchlorider eller blan-35 dinger deraf. For eksempel kalium, lithium-, natrium-, kalcium, strontium- eller ammonium-chlorid.Various metal chlorides or mixtures thereof can be used. For example, potassium, lithium, sodium, calcium, strontium or ammonium chloride.
3 DK 166432 Bl3 DK 166432 Pg
Fortrinsvis anvendes en blanding af aluminiumchlorid og af natriumchlorid i vilkårlig mængde andele, og ikke udelukkende en ækvimolær blanding. Smelten kan ligeledes indeholde lithiumchlorid og/eller kaliumchlorid. Man kan 5 således have en vilkårlig blanding af aluminiumchlorid, af natriumchlorid og af lithiumchlorid.Preferably, a mixture of aluminum chloride and of sodium chloride is used in any proportion, and not exclusively an equimolar mixture. The melt may also contain lithium chloride and / or potassium chloride. Thus, any mixture of aluminum chloride, of sodium chloride and of lithium chloride can be obtained.
Man foretrækker ligeledes, at smelten indeholder mindst 50 molprocent aluminiumchlorid, og at det udviser et 10 smeltepunkt lavere end 200 °C.It is also preferred that the melt contains at least 50 mole percent aluminum chloride and exhibit a melting point lower than 200 ° C.
Opfindelsen er især rettet mod enhver chloreret organisk forbindelse, indeholdende mere end to carbonatomer; men den er først og fremmest nyttig med aliphatiske, cyklis-15 ke, aromatiske monocykliske eller polycykliske og hetero-cykliske forbindelser. Opfindelsen angår ganske særlig perchlorerede, aliphatiske forbindelser samt blandt de aromatiske forbindelser polychlorbiphenyl-derivaterne.In particular, the invention is directed to any chlorinated organic compound containing more than two carbon atoms; but it is primarily useful with aliphatic, cyclic, aromatic monocyclic or polycyclic and heterocyclic compounds. The invention relates particularly to perchlorinated aliphatic compounds as well as to the aromatic compounds the polychlorobiphenyl derivatives.
20 Den mængde chloreret organisk forbindelse, der skal destrueres, er med fordel mindre end 2000 ppm i forhold til smelten.The amount of chlorinated organic compound to be destroyed is preferably less than 2000 ppm relative to the melt.
Disse produkter kan foreligge i vilkårlig form. De kan 25 især befinde sig i en fast fase, f.eks. absorberet på aktivt kul.These products may be in any form. In particular, they may be in a solid phase, e.g. absorbed on activated carbon.
Fremgangsmåden ifølge opfindelsen består i at bringe den chlorerede forbindelse i kontakt med smelten.The process of the invention consists in contacting the chlorinated compound with the melt.
30 Når den chlorerede forbindelse befinder sig i en fast fase, kan man hælde denne faste fase ud i smelten, der fortrinsvis er under omrøring. Man sikrer sig at holde smelten i smeltet tilstand, evt. ved opvarmning. Man går frem · 35 på samme måde, dersom de chlorerede forbindelser er i en væskeformig fase. Mest hyppig befinder de chlorerede forbindelser, som man ønsker at destruere, sig i en enkel 17« DK 166432 Bl 4 gasfase eller i en blanding med let chlorerede forbindelser og/eller bære-gasarter. Det kan f.eks. dreje sig om en gas stammende fra en forbrænding, og man har i så tilfælde nitrogen indeholdende kuldioxyd, mulmonooxyd, chlo-5 rerede forbindelser og evt. oxygen. Men det kan dreje sig om en vilkårlig gasformig blanding taget fra en vilkårlig proces.When the chlorinated compound is in a solid phase, this solid phase can be poured into the melt, which is preferably stirred. You make sure to keep the melt in the molten state, possibly. by heating. · 35 is proceeded in the same way if the chlorinated compounds are in a liquid phase. Most frequently, the chlorinated compounds which one wishes to destroy are present in a single gas phase or in a mixture of slightly chlorinated compounds and / or carrier gases. It can for example. a gas originating from a combustion, and in this case nitrogen containing carbon dioxide, monoxide, chlorinated compounds and possibly oxygen. But it can be any gaseous mixture taken from any process.
Man foretrækker, at de chlorerede forbindelser befinder 10 sig i en vandfri fase. Gassen indeholdende chlorerede forbindelser kan tørres ved kontakt med et absorbtionsmiddel, f.eks. aluminiumoxyd eller glykol.It is preferred that the chlorinated compounds be in an anhydrous phase. The gas containing chlorinated compounds may be dried by contact with an absorbent, e.g. alumina or glycol.
Derpå bringer man denne gasformige fase indeholdende de 15 chlorerede forbindelser, der skal destrueres, i kontakt med smelten ved en vilkårlig anordning til kontaktskabelse mellem en væskeformig fase og en gasformig fase. Dette kan være en kolonne forsynet med bunde eller med fyldning. Man kan ligeledes indføre den gasformige fase i en 20 omrørt beholder med smelten ved hjælp af et neddykket tilførselsrør eller ved hjælp af et rør, som er tilsluttet bunden af beholderen.Then, this gaseous phase containing the 15 chlorinated compounds to be destroyed is brought into contact with the melt by any device for contacting a liquid phase with a gaseous phase. This can be a column with bottoms or a filling. The gaseous phase can also be introduced into a stirred container with the melt by means of a submerged supply tube or by a tube connected to the bottom of the container.
De forskellige chlorerede organiske forbindelser kan for-25 dele sig mellem den flydende fase og dampfasen over smelten. Det samme gælder de forbindelser, der ledsager disse chlorerede forbindelser. Man kan anvende en kolonne med bunde eller med fyldning for at sikre en kontinuerlig cirkulation og omrøring mellem de væskeformige og de gas-30 formige faser og en god kontaktskabelse mellem de gasformige forbindelser og smelten. Man kan ligeledes arbejde med en kaskaderækkefølge af omrørte reaktioner. Man opretholder kontakten mellem de chlorerede organiske forbindelser og smelten i den tid, der er nødvendig for ned-35 brydningen deraf. Opholdstiden kan variere indenfor meget brede rammer; men den er i almindelighed mellem nogle minutter og nogle timer.The various chlorinated organic compounds can be divided between the liquid phase and the vapor phase over the melt. The same applies to the compounds that accompany these chlorinated compounds. A bottom or fill column may be used to ensure continuous circulation and stirring between the liquid and gaseous phases and good contact formation between the gaseous compounds and the melt. You can also work with a cascade sequence of stirred reactions. Contact between the chlorinated organic compounds and the melt is maintained for the time required for its degradation. The residence time can vary within very wide limits; but it is generally between a few minutes and a few hours.
5 DK 166432 B15 DK 166432 B1
Skønt man kan arbejde med enhver temperatur, under forudsætning af at smelten er flydende, foretrækker man at placere sig under 300 °C, fortrinsvis mellem 200 °C og 300 °C.Although one can operate at any temperature, provided the melt is liquid, it is preferable to place below 300 ° C, preferably between 200 ° C and 300 ° C.
55
Nedbrydningshastigheden for de chlorerede forbindelser, især de aromatiske forbindelser, forhøjes med temperaturen af smelten.The rate of degradation of the chlorinated compounds, especially the aromatic compounds, is increased by the temperature of the melt.
10 Man kan finde i gasfasen i smelten lette nedbrydningsprodukter af de chlorerede forbindelser, som man har ønsket af destruere; f.eks. carbontetrachlorid og/hexachloretan.10 One can find in the gas phase in the melt easy decomposition products of the chlorinated compounds which one wishes to destroy; eg. carbon tetrachloride and / hexachloroethane.
Man genfinder ikke i dampfasen i smelten de chlorerede organiske forbindelser, som man ønskede at destruere. Når 15 man analyserer smelten, efter at man har respekteret kontakttiderne mellem chlorerede forbindelser og smelten, genfinder man ikke de organiske forbindelser, som man ønskede at destruere.The vapor phase in the melt does not contain the chlorinated organic compounds which it is desired to destroy. When analyzing the melt after respecting the contact times between chlorinated compounds and the melt, the organic compounds which one wished to destroy were not recovered.
20 Man kan ligeledes periodisk rense smelten for at undgå akkumuleringen af uopløselige forbindelser, der ikke kan forblive i suspension i badet. Under denne rensning genfinder man heller ikke noget spor af de chlorerede organiske forbindelser. Man konstaterer således fraværet af 25 de chlorerede forbindelser, som man ønskede af destruere.It is also possible to periodically purify the melt to avoid the accumulation of insoluble compounds which cannot remain in suspension in the bath. During this purification, no trace of the chlorinated organic compounds is found. Thus, the absence of the chlorinated compounds which one wished to destroy was found.
Ved en foretrukken udøvelsesform for opfindelsen sætter man til smelten et eller flere metaller i pulverform valgt blandt reducerende metaller, såsom f.eks. aluminium 30 og zink. Man foretrækker at anvende et pulver, hvis middelkorn størrelse er mindre end 500 Mm. Dersom man anvender metaller, fjerner man fuldstændig de chlorerede organiske forbindelser ligesom tidligere, men med en klart større hastighed, i størrelsesordenen fra nogle gange til 35 nogle snese gange den tidligere hastighed.In a preferred embodiment of the invention, one or more powdered metals selected from reducing metals are added to the melt, such as e.g. aluminum 30 and zinc. It is preferable to use a powder whose average grain size is less than 500 mm. If metals are used, the chlorinated organic compounds are completely removed as before, but at a much greater rate, on the order of sometimes to 35 some tens of times the previous rate.
DK 166432 B1 6 '*DK 166432 B1 6 '*
Man konstaterer et forbrug af metal-pulveret (eller af metal-pulverne), hvilket kan antyde, at chloridet er blevet dannet under fjernelse af chlor fra de chlorerede organiske forbindelser under destruktionen deraf. Der er 5 ikke nogen grænse for den mængde metal-pulver, der kan indføres i smelten. Man foretrækker at anvende aluminium i pulverform; man kan anbringe op til 5 eller 10 vægtprocent aluminiumpulver i smelten. Man konstaterer, at nedbrydningshastigheden for chlorerede forbindelser stiger 10 med mængden af aluminiumpulver og med temperaturen af smelten. Man foretrækker at omrøre badet, således at metalpulveret er godt dispergeret i badet. Det eller de me-talchlorider, der bliver fremstillet, kan blande sig med smelten og fordele sig mellem den væskeformige fase og 15 den gasformige fase. Man kan om nødvendigt fjerne metal-chlorider fra den gasformige fase ved at behandle denne med et hydroxyd, såsom natriumhydroxyd eller kaliumhy-droxyd.Consumption of the metal powder (or of the metal powders) is found, which may indicate that the chloride has been formed during the removal of chlorine from the chlorinated organic compounds during its destruction. There is no limit to the amount of metal powder that can be introduced into the melt. It is preferred to use aluminum in powder form; up to 5 or 10% by weight of aluminum powder can be placed in the melt. It is found that the rate of degradation of chlorinated compounds increases 10 with the amount of aluminum powder and with the temperature of the melt. It is preferred to stir the bath so that the metal powder is well dispersed in the bath. The metal chloride (s) produced can mix with the melt and distribute between the liquid phase and the gaseous phase. If necessary, metal chlorides can be removed from the gaseous phase by treating it with a hydroxide such as sodium hydroxide or potassium hydroxide.
20 De efterlysende eksempler belyser opfindelsen: EKSEMPEL 1The following examples illustrate the invention: EXAMPLE 1
Man anbringer i en "Pyrex"kolbe på 1 liter, der er elek-25 trisk opvarmet, og som er forsynet med en skrueformet omrører der drejer med 300 omdrejninger pr. minut, 500 g natrium-/aluminiumchlorid, hvori målforholdet erOne is placed in a 1 liter electrically heated "Pyrex" flask which is provided with a helical stirrer rotating at 300 rpm. 500 g of sodium / aluminum chloride in which the target ratio is
AlClg 30 _ = 1AlClg 30 _ = 1
NaClNaCl
Produktet opvarmes til 200 °C, omrøres, hvorpå man indfører 0,2 g hexachlorbenzen og 0,1 g becachlorbiphenyl.The product is heated to 200 ° C, stirred, then 0.2 g of hexachlorobenzene and 0.1 g of becachlorobiphenyl are added.
35 Efter en time ved 200 °C overskyller man det smeltede bad i 15 minutter med N2 i en mængde 50 1/time, idet denne gasart er vasket i et gennemboblingsapparat indeholdende 5 7 DK 166432 B1 100 ml hexat.After one hour at 200 ° C, the molten bath is rinsed with N 2 for 15 minutes at an amount of 50 l / hour, this gas being washed in a bubbling apparatus containing 100 ml of hexate.
Man måler ved gasfasechromatografi de chlorerede organiske forbindelser i badet ved afslutningen såvel i hexanen.Gas phase chromatography measures the chlorinated organic compounds in the bath at the end as well as in the hexane.
De således opnåede resultater er vist i efterfølgende tabel 1.The results thus obtained are shown in subsequent Table 1.
EKSEMPEL 2 10EXAMPLE 2 10
Man gennemfører det samme forsøg, idet man dog yderligere indfører i smelten 5% fint aluminiumpulver (kvaliteten PECHINEY XY 49). Efter en time ved 200 °C efterfulgt af en over skylning på 15 minutter med ^ i mængden 50 1/time 15 udtager man en prøve af badet og af hexaten til analyse.The same experiment is carried out, however, further introducing into the melt 5% fine aluminum powder (quality PECHINEY XY 49). After one hour at 200 ° C, followed by an over rinsing of 15 minutes with 2 in the amount of 50 l / hour 15, a sample of the bath and of the hexate is taken for analysis.
De derved opnåede resultater er ligeledes vist i efterfølgende tabel 1.The results thus obtained are also shown in subsequent Table 1.
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•ri 44 ft Ό u jc m »-i u ω i u fl) <u -H c q > U C ·<Η Φ ID * O <0 X3 cn rH Pj Hc i rH σ> *4 rH cj m x: i-ι o ω ιο u u O ·« Ό U Ω 9 DK 166432 B1 EKSEMPEL 3• ri 44 ft Ό u jc m »-iu ω iu fl) <u -H cq> UC · <Η Φ ID * O <0 X3 cn rH Pj Hc i rH σ> * 4 rH cj mx: i-ι o ω ιο uu O · «Ό U Ω 9 DK 166432 B1 EXAMPLE 3
Man arbejder i det samme apparat, som er anvendt til eksemplerne 1 og 2; men man modificerer driftsbetingelser-5 ne: badets temperatur = 250 °C smeltens vægt: 500 g tilsætning af 5% aluminiumpulver (PECHINEY XY 49) 10 forsøgets varighed: 2 timer overskylning med nitrogen ved afslutningen af de 2 timer: 15 minutter tilsætning fra starten af: 1500 mg hexachlorbenzen 500 mg decachlorbiphenyl.One operates in the same apparatus used for Examples 1 and 2; but operating conditions are modified: the temperature of the bath = 250 ° C weight of the melt: 500 g addition of 5% aluminum powder (PECHINEY XY 49) Duration of the experiment: 2 hours flush with nitrogen at the end of the 2 hours: 15 minutes addition from the start of: 1500 mg hexachlorobenzene 500 mg decachlorobiphenyl.
1515
De derved opnåede resultater er vist i efterfølgende tabel 2.The results thus obtained are shown in subsequent Table 2.
EKSEMPEL 4 20EXAMPLE 4 20
Samme forsøg som eksempel nr. 3, men forsøgets varighed er 4 timer.Same experiment as Example # 3, but the duration of the experiment is 4 hours.
De derved opnåede resultater er ligeledes vist i efter-25 følgende tabel 2. 1 35 10 DK 166432 B1 — —T~ — — — — — — — — —The results thus obtained are also shown in the following Table 2. 1 35 10 DK 166432 B1 - —T ~ - - - - - - - - -
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Φ J0 (X) PΦ J0 (X) P
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rH Dl P rH tn tn O ft * x. p o φ vo vo vo o cn U O <w Ό U U U O ftrH Dl P rH tn tn O ft * x. p o φ vo vo vo o cn U O <w Ό U U U O ft
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8700669 | 1987-01-21 | ||
| FR8700669A FR2609652B1 (en) | 1987-01-21 | 1987-01-21 | PROCESS FOR THE DESTRUCTION OF LOW TEMPERATURE CHLORINE PRODUCTS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK23288D0 DK23288D0 (en) | 1988-01-20 |
| DK23288A DK23288A (en) | 1988-07-22 |
| DK166432B1 true DK166432B1 (en) | 1993-05-24 |
Family
ID=9347122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK023288A DK166432B1 (en) | 1987-01-21 | 1988-01-20 | PROCEDURE FOR DEGREE OF ORGANIC CHLORED COMPOUNDS |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0277858B1 (en) |
| JP (1) | JPS63192468A (en) |
| CN (1) | CN1012142B (en) |
| AT (1) | ATE51531T1 (en) |
| AU (1) | AU610552B2 (en) |
| CA (1) | CA1333404C (en) |
| DE (1) | DE3860064D1 (en) |
| DK (1) | DK166432B1 (en) |
| ES (1) | ES2014508B3 (en) |
| FI (1) | FI880241A (en) |
| FR (1) | FR2609652B1 (en) |
| GR (1) | GR3000437T3 (en) |
| IE (1) | IE60535B1 (en) |
| IN (1) | IN170563B (en) |
| NO (1) | NO174088C (en) |
| NZ (1) | NZ223232A (en) |
| PT (1) | PT86577B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931167A (en) * | 1987-10-13 | 1990-06-05 | Advanced Refinery Technology | Degradation of polychlorinated biphenyls |
| US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
| JP4458585B2 (en) * | 1999-09-09 | 2010-04-28 | 祝治 朝倉 | Methods for decomposing and detoxifying harmful organic compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5257149A (en) * | 1975-11-07 | 1977-05-11 | Gunma Daigakuchiyou | Method of decomposing halogenated aromatic compounds to carboneous substance using molten salts |
| 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 |
-
1987
- 1987-01-21 FR FR8700669A patent/FR2609652B1/en not_active Expired - Lifetime
-
1988
- 1988-01-12 NO NO880104A patent/NO174088C/en unknown
- 1988-01-13 CA CA000556427A patent/CA1333404C/en not_active Expired - Fee Related
- 1988-01-14 ES ES88400074T patent/ES2014508B3/en not_active Expired - Lifetime
- 1988-01-14 DE DE8888400074T patent/DE3860064D1/en not_active Expired - Fee Related
- 1988-01-14 AT AT88400074T patent/ATE51531T1/en not_active IP Right Cessation
- 1988-01-14 EP EP88400074A patent/EP0277858B1/en not_active Expired - Lifetime
- 1988-01-19 JP JP63009439A patent/JPS63192468A/en active Pending
- 1988-01-19 IN IN34/MAS/88A patent/IN170563B/en unknown
- 1988-01-19 NZ NZ223232A patent/NZ223232A/en unknown
- 1988-01-20 PT PT86577A patent/PT86577B/en unknown
- 1988-01-20 CN CN88100299A patent/CN1012142B/en not_active Expired
- 1988-01-20 DK DK023288A patent/DK166432B1/en not_active IP Right Cessation
- 1988-01-20 AU AU10621/88A patent/AU610552B2/en not_active Ceased
- 1988-01-20 IE IE13788A patent/IE60535B1/en not_active IP Right Cessation
- 1988-01-20 FI FI880241A patent/FI880241A/en not_active Application Discontinuation
-
1990
- 1990-04-18 GR GR90400235T patent/GR3000437T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ223232A (en) | 1991-05-28 |
| FI880241A (en) | 1988-07-22 |
| NO174088B (en) | 1993-12-06 |
| GR3000437T3 (en) | 1991-06-28 |
| NO174088C (en) | 1994-03-16 |
| PT86577B (en) | 1991-12-31 |
| ES2014508B3 (en) | 1990-07-16 |
| PT86577A (en) | 1988-02-01 |
| AU1062188A (en) | 1988-07-28 |
| FI880241A0 (en) | 1988-01-20 |
| AU610552B2 (en) | 1991-05-23 |
| ATE51531T1 (en) | 1990-04-15 |
| CN1012142B (en) | 1991-03-27 |
| IN170563B (en) | 1992-04-11 |
| CA1333404C (en) | 1994-12-06 |
| DE3860064D1 (en) | 1990-05-10 |
| DK23288D0 (en) | 1988-01-20 |
| FR2609652B1 (en) | 1992-05-15 |
| NO880104D0 (en) | 1988-01-12 |
| JPS63192468A (en) | 1988-08-09 |
| EP0277858B1 (en) | 1990-04-04 |
| FR2609652A1 (en) | 1988-07-22 |
| IE60535B1 (en) | 1994-07-27 |
| CN88100299A (en) | 1988-08-03 |
| DK23288A (en) | 1988-07-22 |
| EP0277858A1 (en) | 1988-08-10 |
| IE880137L (en) | 1988-07-21 |
| NO880104L (en) | 1988-07-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PBP | Patent lapsed |