EP0442088A1 - Process for the oxidation of water insoluble organic compounds - Google Patents

Process for the oxidation of water insoluble organic compounds Download PDF

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Publication number
EP0442088A1
EP0442088A1 EP90124224A EP90124224A EP0442088A1 EP 0442088 A1 EP0442088 A1 EP 0442088A1 EP 90124224 A EP90124224 A EP 90124224A EP 90124224 A EP90124224 A EP 90124224A EP 0442088 A1 EP0442088 A1 EP 0442088A1
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Prior art keywords
bar
chlorinated
oxidation
oxidised
autoclave
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EP90124224A
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German (de)
French (fr)
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EP0442088B1 (en
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Hans-Helmut Dr. Schwarz
Friedhelm Sahlmen
Otto Dr. Immel
Hanno Dr. Henkel
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Bayer AG
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Bayer AG
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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
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Oxidn. of organic pollutants contg. C, H, O and other elements in bound form is effected by reaction with NHO3 at 150-350 deg.C and 6-350 bar. The process is characterised in that water-insol. chlorinated hydrocarbons are oxidised (SiC). Pref. chlorinated dibenzodioxins and chlorinated dibenzofurnas are oxidised. In an examples, the substance oxidised is (a) a substance called chlophen, (b) 1,1-dichloroethane, or (c) chloranil contg. 15ppm octachlorodibenzo-p-dioxin and 1.2ppm octachlorodibenzofuran. The reaction is effected in an autoclave at 30-100 bar. The HNO3 is used in an amt. of 2-40 (esp. 2.5-7) g per g of pollutant. In an example, a mixt. of 30g chlophen and 910g of 20% HNO3 was heated in a Ta autoclave at 280 deg.C and 86 bar for 2 hr. After cooling, the prod. comprised a clear aq. phase and no oily phase. The aq. phase had a COD of 2.4g/l and contained no chlorinated dibenzo-p-dioxins or dibenzofurans. @(3pp Dwg.No.0/0).

Description

Die Erfindung betrifft ein Verfahren zur Oxidation organischer Schadstoffe, die neben Kohlenstoff, Wasserstoff und Sauerstoff noch andere Elemente in gebundener Form enthalten. Dem Verfahren liegt eine Oxidation mit Salpetersäure bei Temperaturen von 150°C bis 350°C und Drucken von 6 bar bis 350 bar zugrunde.The invention relates to a process for the oxidation of organic pollutants which, in addition to carbon, hydrogen and oxygen, also contain other elements in bound form. The process is based on oxidation with nitric acid at temperatures from 150 ° C to 350 ° C and pressures from 6 bar to 350 bar.

Die Beseitigung organischer Abfälle verursacht in vielen Fällen, besonders wenn diese Substanzen Elemente wie Halogene, Schwefel, Phosphor u.dgl. enthielten, große Schwierigkeiten. Bei der häufig benutzten Verbrennung als Entsorgungsmaßnahme müssen z.B. aus den Verbrennungsgasen die Abbauprodukte dieser Elemente mit erheblichem Aufwand ausgewaschen werden. Besondere Schwierigkeiten entstehen dann, wenn die Verbrennung zur Bildung der chlorierten Benzodioxine und Di-benzofurane führt und diese Verbindungen praktisch vollständig entfernt werden müssen.The disposal of organic waste causes in many cases, especially when these substances include elements such as halogens, sulfur, phosphorus and the like. contained great difficulties. In the case of the frequently used incineration as a disposal measure, the decomposition products of these elements have to be washed out of the incineration gases with considerable effort. Particular difficulties arise when the combustion leads to the formation of the chlorinated benzodioxins and di-benzofurans and these compounds have to be removed virtually completely.

Große Probleme entstehen bei der Entgiftung von polychlorierten Biphenylen und Dibenzodioxinen, für deren Abbau eine Vielzahl, in der Regel komplizierte und aufwendige Verfahren entwickelt worden sind. Beispiele hierfür sind die Hochtemperaturverbrennung (Kokoszka, I., und Kuntz, G.: Methods of PCB Disposal, PCB Seminar Sept. 20, 1983, Netherlands, Ministry of Housing and Environment), welche besondere Maßnahmen erfordert, um allen Gasmolekülen eine ausreichende Verweilzeit bei hohen Temperaturen zu ermöglichen. Eine Photolyse (Esposito, M.P., et al.: Dioxins, EPA-Report 600-2-80-197, Nov. 1980) besitzt den gravierenden Nachteil, daß alle zu zerstörenden Moleküle vom Licht getroffen werden müssen. Eine Natriumbehandlung (Goodyear Tire and Rubber Co.: A Safe, ETH Chemical Disposal Method for PCB's, Research Lab., Report 1980) oder die Reaktionen mit Natriumnaphthalenid (Smith, J.G. et al.; J. chem. Technol. Biotechnol 30 (1080) 620) oder mit Alkalimetallpolyethylenglykolaten (Pytlewski, L.I. et al.: Mid Atl. Waste Conf.(Proc.) 1979, 11, 97 C.A. 94 (1981) 14, 108 583) erfordern den nicht einfachen Umgang mit metallischem Natrium. Katalytische Verfahren (Bayer, S.K. et al., Tetrahedron Letters 26, 19 3677) sind nur dann wirtschaftlich, wenn es gelingt, Katalysatoren mit langer Lebensdauer zu entwickeln. Eine Forderung, die häufig nicht oder nur unvollkommen zu erfüllen ist, besonders dann, wenn es sich um verschmutzte Abfallstoffe handelt. Eine radiolytische Zerstörung (Singh, A, et al.: Radiat. Phys. Chem. 24 (1985) 11) und Zersetzung in überkritischem Wasser (Freeman, H.M. und Oletsey, R.A.: J. Air Pollut. Control Assoc. 36 (1986) 11, 1, S. 67) sind ebenfalls Verfahren, die einen sehr hohen technischen Aufwand erfordern.Major problems arise in the detoxification of polychlorinated biphenyls and dibenzodioxins, for the degradation of which a large number, generally complicated and expensive, processes have been developed. Examples of this are high-temperature combustion (Kokoszka, I., and Kuntz, G .: Methods of PCB Disposal, PCB Seminar Sept. 20, 1983, Netherlands, Ministry of Housing and Environment), which requires special measures to ensure that all gas molecules have a sufficient residence time to allow at high temperatures. Photolysis (Esposito, MP, et al .: Dioxins, EPA Report 600-2-80-197, Nov. 1980) has the serious disadvantage that all molecules to be destroyed must be hit by the light. Sodium treatment (Goodyear Tire and Rubber Co .: A Safe, ETH Chemical Disposal Method for PCB's, Research Lab., Report 1980) or the reactions with sodium naphthalenide (Smith, JG et al .; J. chem. Technol. Biotechnol 30 (1080 ) 620) or with alkali metal polyethylene glycolates (Pytlewski, LI et al .: Mid Atl. Waste Conf. (Proc.) 1979, 11, 97 CA 94 (1981) 14, 108 583) require the difficult handling of metallic sodium. Catalytic processes (Bayer, SK et al., Tetrahedron Letters 26, 19 3677) are only economical if it is possible to develop catalysts with a long service life. A requirement that often cannot be met or can only be met incompletely, especially when it comes to contaminated waste. Radiolytic destruction (Singh, A, et al .: Radiat. Phys. Chem. 24 (1985) 11) and decomposition in supercritical water (Freeman, HM and Oletsey, RA: J. Air Pollut. Control Assoc. 36 (1986) 11, 1, p. 67) are also processes that require a very high technical outlay.

Es besteht nach wie vor das Bedürfnis nach einem wirtschaftlichen Entsorgungsverfahren für organische, wasserunlösliche Produkte, die Elemente außer C, H und O enthalten.There is still a need for an economical disposal method for organic, water-insoluble products that contain elements other than C, H and O.

Es wurde gefunden, daß man wasserunlösliche chlorierte Kohlenwasserstoffe weitgehend abbauen kann, wenn man diese Verbindungen mit Salpetersäure vermischt und bei Drucken von 6 bar bis 350 bar auf Temperaturen von 150°C bis 350°C erhitzt.It has been found that water-insoluble chlorinated hydrocarbons can be largely degraded if these compounds are mixed with nitric acid and heated to temperatures of 150 ° C. to 350 ° C. at pressures from 6 bar to 350 bar.

Vorzugsweise wird bei einer Temperatur zwischen 250 und 310°C gearbeitet. Ein Abbau der Substanzen läßt sich dann in einer kurzen Reaktionszeit verwirklichen, wobei der zur Aufrechterhaltung einer flüssigen Phase erforderliche Druck nicht unnötig hoch sein soll. Bei einer Temperatur von 250°C beträgt der minimale Betriebsdruck vorzugsweise ca. 30 bar und bei einer Temperatur von 320°C 100 bar.Is preferably carried out at a temperature between 250 and 310 ° C. Degradation of the substances can then be achieved in a short reaction time, and the pressure required to maintain a liquid phase should not be unnecessarily high. At a temperature of 250 ° C the minimum operating pressure is preferably approximately 30 bar and at a temperature of 320 ° C 100 bar.

Die Konzentration der zur Oxidation eingesetzten Salpetersäure kann in weiten Grenzen variieren. Vorzugsweise wird eine 20 bis 70 %ige Säure eingesetzt. Aber auch die Verwendung höherkonzentrierter Säure ist möglich.The concentration of the nitric acid used for the oxidation can vary within wide limits. A 20 to 70% acid is preferably used. But the use of more concentrated acid is also possible.

Die Reaktionszeit hängt von der Temperatur, der Salpetersäurekonzentration und von der Durchmischung der Komponenten ab. Von besonderer Bedeutung ist die Beobachtung, daß auch bei nicht durchmischten Autoklavenversuchen ein Abbau der organischen Substanz mit Salpetersäure eintritt, wenn er auch langsamer abläuft als bei intensiver Rührung.The reaction time depends on the temperature, the nitric acid concentration and the mixing of the Components. Of particular importance is the observation that even when the autoclave is not mixed, the organic substance decomposes with nitric acid, even if it proceeds more slowly than with intensive stirring.

Um einen vollständigen Abbau der organischen Substanz zu erreichen, ist es zweckmäßig, einen Überschuß an Salpetersäure einzusetzen. 2 g HNO₃ (100 %ig) pro Gramm organischer Substanz bis 40 g/g können zum Abbau der Schadstoffe eingesetzt werden. Vorzugsweise werden 2,5 bis 7 g/g benutzt.In order to achieve a complete breakdown of the organic substance, it is advisable to use an excess of nitric acid. 2 g HNO₃ (100%) per gram of organic substance up to 40 g / g can be used to break down the pollutants. Preferably 2.5 to 7 g / g are used.

Mit dem erfindungsgemäßen Verfahren lassen sich organische Produkte vollkommen abbauen, ohne daß neue Gefahrenstoffe entstehen. Von besonderer Bedeutung ist die Fähigkeit selbst, die sehr beständigen chlorierten Dibenzodioxine und -furane zu zerstören.With the method according to the invention, organic products can be completely broken down without new hazardous substances being produced. Of particular importance is the ability to destroy the very stable chlorinated dibenzodioxins and furans.

Das erfindungsgemäße Verfahren kann sowohl kontinuierlich als auch diskontinuierlich durchgeführt werden.The process according to the invention can be carried out either continuously or batchwise.

Beispiel 1example 1

30 g Chlophen und 910 g 20 %ige Salpetersäure werden in einem Schüttelautoklaven aus Tantal bei einem Druck von 86 bar 2 Stunden auf 280°C erhitzt. Nach dem Abkühlen bleibt eine klare wäßrige Phase über. Die ursprünglich vorhandene ölige Chlophenphase ist völlig verschwunden. Die wäßrige Phase besitzt einen CSB-Wert von 2,4 g/l. In der wäßrigen Phase sind keine chlorierten Dibenzo-p-dioxine und Dibenzofurane nachweisbar.30 g of chlorophene and 910 g of 20% nitric acid are heated in a tantalum shaking autoclave at 280 bar for 2 hours at a pressure of 86 bar. After cooling, a clear aqueous phase remains. The originally existing oily chlorophene phase has completely disappeared. The aqueous phase has a COD of 2.4 g / l. No chlorinated dibenzo-p-dioxins and dibenzofurans are detectable in the aqueous phase.

Beispiel 2Example 2

60 g Chlophen mit 44,8 Gew.-% organisch gebundenem Chlor wird mit 910 g 40 %iger Salpetersäure 4 Stunden auf 250°C im Autoklaven bei einem Druck von 46 bar erhitzt. Es resultiert eine einphasige wäßrige Lösung, aus der mit 5-facher Toluolextraktion Verbindungen abgetrennt werden können, die insgesamt noch 0,21 g organisch gebundenes Halogen enthalten. Dies entspricht einer organischen Halogen-Abbaurate von 99,2 %.60 g of chlorophen with 44.8% by weight of organically bound chlorine is heated with 910 g of 40% nitric acid for 4 hours at 250 ° C. in an autoclave at a pressure of 46 bar. The result is a single-phase aqueous solution from which 5-fold toluene extraction can be used to remove compounds which still contain a total of 0.21 g of organically bound halogen. This corresponds to an organic halogen degradation rate of 99.2%.

Beispiel 3Example 3

50 g 1,1-Dichlorethan werden mit 685 g 20 %iger Salpetersäure 2 Stunden auf 280°C bei einem Druck von 94 bar erhitzt. Nach dem Abkühlen resultiert eine klare, wäßrige Phase mit einem CSB-Gehalt von 1 g/l. Dichlorethan kann nicht nachgewiesen werden.50 g of 1,1-dichloroethane are heated with 685 g of 20% nitric acid to 280 ° C. for 2 hours at a pressure of 94 bar. After cooling, a clear, aqueous phase with a COD content of 1 g / l results. Dichloroethane cannot be detected.

Beispiel 4Example 4

5 g Chloranil mit einem Gehalt von 15 ppm Octachlordibenzo-p-dioxin (OCDD) und 1,2 ppm Octachlordibenzofuran wurde mit 910 g 20 %iger Salpetersäure 4 Stunden auf 280°C bei einem Druck von 106 bar erhitzt. Es resultierte eine einheitliche wäßrige Phase, in der weder Chloranil noch polychlorierte Dibenzo-p-dioxine oder polychlorierte Dibenzofurane nachweisbar waren.5 g of chloranil with a content of 15 ppm octachlorodibenzo-p-dioxin (OCDD) and 1.2 ppm octachlorodibenzofuran was heated with 910 g 20% nitric acid at 280 ° C. for 4 hours at a pressure of 106 bar. The result was a uniform aqueous phase in which neither chloranil nor polychlorinated dibenzo-p-dioxins or polychlorinated dibenzofurans were detectable.

Beispiel 5Example 5

30 g Chlophen und 960 g 20 %ige Salpetersäure werden in einem Autoklaven bei einem Druck von 111 bar ohne jede Durchmischung 2 h auf 280°C erhitzt. Beim Abkühlen resultiert nur eine wäßrige Phase, deren CSB-Wert 1,4 g/l beträgt.30 g of chlorophene and 960 g of 20% nitric acid are heated in an autoclave to 280 ° C. for 2 hours without any mixing at a pressure of 111 bar. On cooling, only an aqueous phase results, the COD value of which is 1.4 g / l.

Claims (4)

Verfahren zur Oxidation organischer Schadstoffe, die neben Kohlenstoff, Wasserstoff und Sauerstoff noch andere Elemente in gebundener Form enthalten durch Oxidation mit Salpetersäure bei Temperaturen von 150°C bis 350°C und Drucken von 6 bar bis 350 bar, dadurch gekennzeichnet, daß wasserunlösliche chlorierte Kohlenwasserstoffe oxidiert werden.Process for the oxidation of organic pollutants which, in addition to carbon, hydrogen and oxygen, also contain other elements in bound form by oxidation with nitric acid at temperatures from 150 ° C to 350 ° C and pressures from 6 bar to 350 bar, characterized in that water-insoluble chlorinated hydrocarbons be oxidized. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß mit einem Überschuß von 2 g bis 40 g Salpetersäure, vorzugsweise 2,5 g bis 7 g pro Gramm Schadstoff gearbeitet wird.A method according to claim 1, characterized in that an excess of 2 g to 40 g nitric acid, preferably 2.5 g to 7 g per gram of pollutant is used. Verfahren nach Anspruch 1 bis 2, dadurch gekennzeichnet, daß die Oxidation in einem Autoklaven bei Drucken zwischen 30 bar und 100 bar durchgeführt wird.Process according to Claims 1 to 2, characterized in that the oxidation is carried out in an autoclave at pressures between 30 bar and 100 bar. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß chlorierte Dibenzodioxine und chlorierte Dibenzofurane oxidiert werden.Process according to Claims 1 to 3, characterized in that chlorinated dibenzodioxins and chlorinated dibenzofurans are oxidized.
EP90124224A 1990-01-23 1990-12-14 Process for the oxidation of water insoluble organic compounds Expired - Lifetime EP0442088B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4001782A DE4001782A1 (en) 1990-01-23 1990-01-23 Oxidn. of chlorinated organic pollutants - by reaction with nitric acid at high temp. and pressure
DE4001782 1990-01-23

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EP0442088A1 true EP0442088A1 (en) 1991-08-21
EP0442088B1 EP0442088B1 (en) 1993-04-21

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US (1) US5174985A (en)
EP (1) EP0442088B1 (en)
AT (1) ATE88368T1 (en)
DE (2) DE4001782A1 (en)
DK (1) DK0442088T3 (en)
ES (1) ES2055284T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503387A1 (en) * 1991-03-13 1992-09-16 BASF Aktiengesellschaft Process for decomposition of aromatic nitro compounds contained in waste water

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
US5799257A (en) * 1992-10-27 1998-08-25 Lockheed Martin Idaho Technologies Company Process for gamma ray induced degradation of polychlorinated biphenyls
US5454844A (en) * 1993-10-29 1995-10-03 Minnesota Mining And Manufacturing Company Abrasive article, a process of making same, and a method of using same to finish a workpiece surface
US6973678B2 (en) 2002-03-13 2005-12-13 Jones Timothy B Easily assembled specimen container

Citations (1)

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US4080168A (en) * 1976-02-18 1978-03-21 The Curators Of The University Of Missouri Method and apparatus for the wet digestion of organic and biological samples

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US4497782A (en) * 1982-10-28 1985-02-05 S. Garry Howell Method for destroying toxic organic chemical products
US5019175A (en) * 1989-05-11 1991-05-28 The United States Of America As Represented By The Administrator, Environmental Protection Agency Method for the destruction of halogenated organic compounds in a contaminated medium
US4995916A (en) * 1990-04-30 1991-02-26 The United States Of America As Represented By The United States Department Of Energy Method of recovering hazardous waste from phenolic resin filters

Patent Citations (1)

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Non-Patent Citations (1)

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503387A1 (en) * 1991-03-13 1992-09-16 BASF Aktiengesellschaft Process for decomposition of aromatic nitro compounds contained in waste water
US5232605A (en) * 1991-03-13 1993-08-03 Basf Aktiengesellschaft Breakdown of waste waters containing aromatic nitro compounds

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Publication number Publication date
DE4001782A1 (en) 1991-07-25
ES2055284T3 (en) 1994-08-16
ATE88368T1 (en) 1993-05-15
US5174985A (en) 1992-12-29
DK0442088T3 (en) 1993-05-17
EP0442088B1 (en) 1993-04-21
DE59001261D1 (en) 1993-05-27

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