EP0617985A1 - Procédé pour la déhalogénation des hydrocarbons aromatiques halogénés - Google Patents

Procédé pour la déhalogénation des hydrocarbons aromatiques halogénés Download PDF

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Publication number
EP0617985A1
EP0617985A1 EP94104151A EP94104151A EP0617985A1 EP 0617985 A1 EP0617985 A1 EP 0617985A1 EP 94104151 A EP94104151 A EP 94104151A EP 94104151 A EP94104151 A EP 94104151A EP 0617985 A1 EP0617985 A1 EP 0617985A1
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EP
European Patent Office
Prior art keywords
carried out
hydrothermal treatment
filter
minutes
dusts
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.)
Withdrawn
Application number
EP94104151A
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German (de)
English (en)
Inventor
Roland Dr. Thome
Hubert Ing. Chem. Bings
Thomas Dr. Ade
Gerhard Dr. Kudermann
Jürgen Dipl.-Ing. Schubert
Hans-Paul Prof. Dr. Hagenmaier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vereinigte Aluminium Werke AG
Vaw Aluminium AG
Original Assignee
Vereinigte Aluminium Werke AG
Vaw Aluminium AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE4313266A external-priority patent/DE4313266A1/de
Application filed by Vereinigte Aluminium Werke AG, Vaw Aluminium AG filed Critical Vereinigte Aluminium Werke AG
Publication of EP0617985A1 publication Critical patent/EP0617985A1/fr
Withdrawn legal-status Critical Current

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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
    • A62D3/20—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by hydropyrolysis or destructive steam gasification, e.g. using water and heat or supercritical water, to effect chemical change
    • 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

Definitions

  • the invention relates to a process for the dehalogenation of halogenated aromatic hydrocarbons, in particular of solids loaded with polyhalogenated dibenzodioxins and / or furans.
  • a special object of the present invention is to destroy the organic halogen compounds which occur in the filter dusts of remelting plants in the non-ferrous metal industry and adhere to the filter aids and to make the lime dusts used as filter aids usable again for exhaust gas purification after the organic chlorides have been destroyed, the calcium chloride crystallize from the solutions, activate them and use them as drying agents, for example.
  • halogenated aromatic hydrocarbons bound to solids which contain polyhalogenated dibenzodioxins and / or furans, are treated hydrothermally in aqueous suspensions or in solutions, the temperatures between 150-330 ° C. and the residence times between 5 and 200 minutes lie.
  • the polyhalogenated dibenzodioxins and furans are hydrolytically dehalogenated with a particularly high effect at temperatures of 250 - 330 ° C if the pH is greater than 7.
  • the halides split off go into solution and are separated off by crystallization in a subsequent step.
  • the method is also applicable to filter dusts from waste or special waste incineration plants as well as on contaminated soils.
  • the process is preferably carried out in continuously operating tubular reactors in which the aqueous suspension of contaminated dusts (30-300g / l solids content) is heated to 250-330 ° C in a few minutes with turbulent flow and after a residence time of 10-15 minutes Temperature is cooled to below the boiling point.
  • This information relates to both coal and lime-containing solids, with lime-containing solids according to the invention being filtered off after the hydrothermal treatment, dried and returned to the exhaust gas purification as calcium hydroxide.
  • lime-containing solids according to the invention being filtered off after the hydrothermal treatment, dried and returned to the exhaust gas purification as calcium hydroxide.
  • calcium chloride is crystallized out of the filtrate and, after filtration and drying, used as a drying agent.
  • the recycled filter dusts can be returned to the filter system after they have been broken down by more than 90%.
  • the process conditions according to the invention have a temperature range of 150-330 ° C. with a residence time of 5-200 minutes. Above the specified temperature limit, the reaction temperature approaches the critical temperature, while at temperatures below 150 ° C the reaction times are too long for an industrial process to achieve a reasonable space / time yield.
  • the process according to the invention is a hydrolytic dehalogenation which can take place under reducing and oxidizing conditions in a hydrogen or oxygen atmosphere.
  • the additives according to the invention must be metered in such a way that the lower explosion limit of oxyhydrogen is reliably avoided by hydrogen being released.
  • filter dust is mixed with water with addition of the additives according to the invention, heated and, after the reaction temperature has been reached, subjected to a residence time in accordance with the conditions specified in the process claims.
  • the filtration is carried out with subsequent drying of the solid.
  • Calcium chloride is crystallized out of the filtrate and the residual water is circulated.
  • a suspension of filter dust (analysis in FIG. 3) and water with a solids content of 300 g per liter was produced.
  • 3 g / l of metallic aluminum were added to the suspension.
  • the mixture was then heated in an autoclave under an air atmosphere to 270 ° C. in 50 minutes. After a dwell time of 20 minutes, the mixture was cooled to 50 ° C.
  • column 1 it can be seen that a degree of degradation of 90% can be achieved.
  • Filter dust (Fig. 3) was treated as in Example 1, but additionally covered with oxygen.
  • the analysis result (Fig. 7, column 2) shows that additional oxygen has no positive influence on the breakdown of the polyhalogenated dibenzodioxins and furans.
  • a suspension was prepared as in the previous examples and heated to 270 ° C. in an autoclave in a hydrogen atmosphere in 50 minutes.
  • the analysis results of the residue show, according to FIG. 7, column 3, that additional hydrogen does not bring any improvement for the decomposition of the organic chlorides.
  • a suspension of filter dust and water with a solids content of 300 g / l was heated to 270 ° C. in an air atmosphere in 50 minutes without the additional addition of aluminum. After a residence time of 20 minutes, the suspension was cooled to 50 ° C. and the residue was filtered off.
  • the analysis of the residue shows that although the organic chlorides are degraded, the degradation rate (FIG. 7, column 4) is, however, significantly lower than in example 1.
  • a suspension of filter dust (analysis in FIG. 3) and water with a solids content of 100 g / l and a copper sulfate addition of 1.5 g / l was heated to 270 ° C. in an oxygen atmosphere in 50 minutes. After a residence time of 20 minutes, the mixture was cooled to 50 ° C. and the residue was filtered off.
  • the analysis of the residue shows that the addition of copper sulfate and oxygen causes an increase in the degradation rate compared to Example 4.
  • Filter dust (Fig. 3) was treated as in Example 1, but not heated to 270 ° C but to 300 ° C in about 55 minutes. After a dwell time of 20 minutes, the mixture was cooled to 50 ° C. The degree of degradation of 94%, shown in Fig. 7, column 7, shows the positive influence of elevated temperature.
  • Filter dust (analysis in Fig. 4) was stirred with water and 3 g / l aluminum was added.
  • the solids content of the suspension was 300 g / l (pH> 7).
  • the suspension was heated to 300 ° C. in 55 minutes, held at this temperature for 20 minutes and then cooled to 50 ° C.
  • the degree of degradation (FIG. 7, column 9) of the contents of polyhalogenated dibenzodioxins / furans was 93%.
  • Filter dust (FIG. 5) was mixed with water and, after addition of 1.5 g / l copper sulfate in an autoclave, heated to 300 ° C. under oxygen in 55 minutes. After a dwell from 20 minutes was cooled to 50 ° C. The degree of degradation at 1.2.3.4-TCDD (Fig. 7, column 11) was 98%.
  • Coke-containing filter dust (analysis in Fig. 6) was mixed with water and 3 g / l aluminum was added.
  • the solids content of the suspension was 300 g / l (pH> 7).
  • the suspension was heated to 300 ° C. in 55 minutes, held at this temperature for 20 minutes and then cooled to 50 ° C.
  • the degree of degradation of the contents of polyhalogenated dibenzodioxins / furans (FIG. 7, column 12) was 85%.
  • a suspension of filter dust (analysis in FIG. 3) and water with a solids content of 100 g / l and a copper sulfate addition of 1.5 g / l and an additional 150 g / l sodium aluminate was heated to 330 ° C. in 60 minutes without additional oxygen . After a dwell time of 20 minutes, the mixture was cooled to 50 ° C. The degradation rate could be improved compared to Example 6 by increasing the temperature to 99%.

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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)
  • Processing Of Solid Wastes (AREA)
EP94104151A 1993-03-27 1994-03-17 Procédé pour la déhalogénation des hydrocarbons aromatiques halogénés Withdrawn EP0617985A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4310064 1993-03-27
DE4310064 1993-03-27
DE4313266A DE4313266A1 (de) 1993-03-27 1993-04-23 Verfahren zur Dehalogenierung von halogenierten aromatischen Kohlenwasserstoffen
DE4313266 1993-04-23

Publications (1)

Publication Number Publication Date
EP0617985A1 true EP0617985A1 (fr) 1994-10-05

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ID=25924422

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Application Number Title Priority Date Filing Date
EP94104151A Withdrawn EP0617985A1 (fr) 1993-03-27 1994-03-17 Procédé pour la déhalogénation des hydrocarbons aromatiques halogénés

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EP (1) EP0617985A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1421976A1 (fr) * 2002-11-04 2004-05-26 Terra-Kleen Response Group, Inc. Méthode de traitement des cendres d'incinération contaminées du dioxine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002268A1 (fr) * 1986-09-24 1988-04-07 Boelsing Friedrich Procede pour deshalogener des hydrocarbures
DE3810707A1 (de) * 1988-03-26 1989-10-05 Johannes Mandl Verfahren zur entsorgung organischer chlorverbindungen durch reaktion mit metallen bzw. oxyden, unter bildung von metallchloriden
US5039350A (en) * 1990-04-27 1991-08-13 The United States Of America As Represented By The Administrator Of The Environmental Protection Agency Method for the decomposition of halogenated organic compounds in a contaminated medium
US5197823A (en) * 1992-01-08 1993-03-30 Reynolds Metals Company Method and apparatus for treating PCB-containing soil
DE4207943A1 (de) * 1992-03-12 1993-09-16 Srl Sommer Recycling Lauta Gmb Verfahren zur aufarbeitung al-haltiger pcdd/pcdf-belasteter reststoffe

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002268A1 (fr) * 1986-09-24 1988-04-07 Boelsing Friedrich Procede pour deshalogener des hydrocarbures
DE3810707A1 (de) * 1988-03-26 1989-10-05 Johannes Mandl Verfahren zur entsorgung organischer chlorverbindungen durch reaktion mit metallen bzw. oxyden, unter bildung von metallchloriden
US5039350A (en) * 1990-04-27 1991-08-13 The United States Of America As Represented By The Administrator Of The Environmental Protection Agency Method for the decomposition of halogenated organic compounds in a contaminated medium
US5197823A (en) * 1992-01-08 1993-03-30 Reynolds Metals Company Method and apparatus for treating PCB-containing soil
DE4207943A1 (de) * 1992-03-12 1993-09-16 Srl Sommer Recycling Lauta Gmb Verfahren zur aufarbeitung al-haltiger pcdd/pcdf-belasteter reststoffe

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1421976A1 (fr) * 2002-11-04 2004-05-26 Terra-Kleen Response Group, Inc. Méthode de traitement des cendres d'incinération contaminées du dioxine

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