EP0635283B1 - Procédé pour la déshalogénation réductive des matériaux solides contenant des composés organiques halogénés - Google Patents

Procédé pour la déshalogénation réductive des matériaux solides contenant des composés organiques halogénés Download PDF

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Publication number
EP0635283B1
EP0635283B1 EP94250184A EP94250184A EP0635283B1 EP 0635283 B1 EP0635283 B1 EP 0635283B1 EP 94250184 A EP94250184 A EP 94250184A EP 94250184 A EP94250184 A EP 94250184A EP 0635283 B1 EP0635283 B1 EP 0635283B1
Authority
EP
European Patent Office
Prior art keywords
sodium
minutes
process according
ammonia
solid
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.)
Revoked
Application number
EP94250184A
Other languages
German (de)
English (en)
Other versions
EP0635283A1 (fr
Inventor
Frank-Dieter Kopinke
Matthias Remmler
Ulrich Stottmeister
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.)
Helmholtz Zentrum fuer Umweltforschung GmbH UFZ
Original Assignee
Helmholtz Zentrum fuer Umweltforschung GmbH UFZ
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6493654&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0635283(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Helmholtz Zentrum fuer Umweltforschung GmbH UFZ filed Critical Helmholtz Zentrum fuer Umweltforschung GmbH UFZ
Publication of EP0635283A1 publication Critical patent/EP0635283A1/fr
Application granted granted Critical
Publication of EP0635283B1 publication Critical patent/EP0635283B1/fr
Anticipated expiration legal-status Critical
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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
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • the invention relates to a chemical process for Dahalogenation of halogenated hydrocarbons in Mixtures of solids are included.
  • U.S. Pa. 4 255 252 (1979) is sodium as Suspension (average particle diameter below 100 ⁇ m, preferably below 30 ⁇ m) in oil at elevated temperatures (90 - 160 ° C) with pretreated waste oils for reaction brought.
  • Kennedy et al. Employee M.V. Kennedy, E.J. Stojanovic, F.L. Shuhman, Jr .: Chemical and thermal aspecs of pesticide disposal. J. Environ. Qual. 1972 (1) 63 - 65) describe sodium in ammonia as an agent for destruction of halogenated pesticides previously dissolved in n-hexane were. The authors do not give quantitative ratios (Sodium to pesticide) and use the agent exclusively to previously dissolved (liquid) substances.
  • An advantage of the sodium process is its selectivity. In contrast to oxidative degradation and catalytic Hydrocarbons do not become hydrogenation affected. Because of its high reactivity, sodium even at low temperatures and short reaction times cause complete dehalogenation, if there is no transport limitation in the reaction medium. The technical implementation of the sodium process requires one comparatively low investment and is therefore particularly suitable for smaller, possibly mobile systems.
  • a obvious disadvantage of using metal suspensions is that solid products are not in can be treated easily because solid-to-solid reactions have a high level of transport inhibition. However, this application is of interest for the treatment of solids such as loaded activated carbon and coke, Filter dust u. a. at which low concentrations of more or less tightly bound halogenated hydrocarbons a solid matrix.
  • EP-A 288 408 describes a process for reductive dehalogenation Contaminated solids known for the sodium at - 50 ° C in ammonia is dissolved and the solids with the sodium solution prepared be contacted.
  • the invention solves the problem, halogenated hydrocarbons, which are sorbed on solid matrices, a direct one To make dehalogenation accessible with sodium, being for a largely complete dehalogenation only a small stoichiometric excess of sodium is required.
  • the method can be in different embodiments be applied.
  • the solid is suspended in ammonia and the metallic Sodium added.
  • the dehalogenation is completed after a short reaction time. Nearly Complete sales occur after just a minute of contact between sodium suspension and a little porous Solid matrix.
  • Treatment can be close to temperatures the boiling point of ammonia at atmospheric pressure or at Temperatures close to ambient temperature under increased pressure or executed under conditions between these key points become.
  • the invention has process engineering View specific advantages and disadvantages, in particular the Reactor design and the ammonia circuit concern.
  • the Solvent ammonia can either after the reaction separated from the purified solid as a liquid phase or be vaporized directly. The evaporation is in Dependence on the reaction conditions by heating and / or relaxation achieved. In any case, ammonia circulated.
  • reaction temperatures above 30 ° C only make sense if if this causes additional effects on the solid matrix are to be effected (e.g. extraction of further Pollutants).
  • the workup of the reaction products is of the chosen embodiment and the one to be cleaned Waste product dependent. It contains the following steps that can be combined differently in their order can: (i) decompose excess sodium by Add water or other active hydrogen reagents (e.g. methanol, acetic acid, dilute mineral acids o. a.): (ii) Evaporation of the solvent by Warm up or relax, taking the vaporized ammonia after re-liquefaction is to be circulated; (iii) washing and neutralizing the purified solid or the wash water, if necessary.
  • active hydrogen reagents e.g. methanol, acetic acid, dilute mineral acids

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Extraction Or Liquid Replacement (AREA)

Claims (5)

  1. Procédé pour la déhalogénation par réduction d'hydrocarbures halogénés présents dans des mélanges contenant des matières solides, lequel prévoit un traitement par le sodium de ces mélanges dans de l'ammoniac liquide, caractérisé en ce qu'on ajoute du sodium métallique, dispersé dans de l'ammoniac liquide, à un solide contaminé et que ledit sodium métallique, à l'état dissous, subit d'autres réactions chimiques.
  2. Procédé selon la revendication 1 caractérisé en ce qu'on procède au traitement par le sodium pendant 1-30 minutes, de préférence 2-10 minutes, à la hauteur du recyclage, ce à une température comprise entre 15 et 25 °C et à une pression élevée.
  3. Procédé selon la revendication 1 caractérisé en ce qu'on procède au traitement par le sodium pendant 1-20 minutes, de Préférence 2-10 minutes, sans pression à une température de -33 °C et à une pression légèrement supérieure pour une température inférieure à 0 °C.
  4. Procédé selon la revendication 1 caractérisé en ce qu'on procède au traitement avec un excédent de sodium et que, préalablement à une décomposition avec des composés actifs dans l'hydrogène et en vue d'autres transformations, on isole sous la forme d'une solution ammoniacale le réactif non utilisé.
  5. Procédé selon la revendication 1 caractérisé en ce qu'à la fin de la réaction, on évapore le solvant ammoniac en le réchauffant et/ou le détendant et qu'on l'introduit dans le cycle.
EP94250184A 1993-07-24 1994-07-20 Procédé pour la déshalogénation réductive des matériaux solides contenant des composés organiques halogénés Revoked EP0635283B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4324931 1993-07-24
DE4324931A DE4324931A1 (de) 1993-07-24 1993-07-24 Verfahren zur reduktiven Dehalogenierung von organohalogenhaltigen festen und flüssigen Stoffen

Publications (2)

Publication Number Publication Date
EP0635283A1 EP0635283A1 (fr) 1995-01-25
EP0635283B1 true EP0635283B1 (fr) 1999-01-20

Family

ID=6493654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94250184A Revoked EP0635283B1 (fr) 1993-07-24 1994-07-20 Procédé pour la déshalogénation réductive des matériaux solides contenant des composés organiques halogénés

Country Status (3)

Country Link
EP (1) EP0635283B1 (fr)
AT (1) ATE175882T1 (fr)
DE (2) DE4324931A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0880378A4 (fr) * 1995-11-07 1999-03-24 Commodore Applied Technologies Procede et equipement de destruction d'agents de guerre chimique
JP2003230638A (ja) * 2002-02-07 2003-08-19 Toshiba Corp 有害有機塩素化合物の無害化処理システムおよび無害化処理された生成物と廃棄物のリサイクル方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2249679C3 (de) * 1972-10-11 1980-09-11 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von 9cis Tricosen, Muscalure
DE2813200C2 (de) * 1978-03-25 1986-03-27 Degussa Ag, 6000 Frankfurt Verfahren zur Wiederaufbereitung von gebrauchten Schmierölen
US4910353A (en) * 1983-02-07 1990-03-20 Transformer Service, Inc. Dehalogenation of polychlorinated biphenyls and other related compounds
CH668709A5 (de) * 1985-12-06 1989-01-31 Ciba Geigy Ag Verfahren zur enthalogenierung von polyhalogenierten aliphatischen und aromatischen verbindungen.
US4853040A (en) * 1987-03-30 1989-08-01 A. L. Sandpiper Corporation Processes for decontaminating polluted substrates

Also Published As

Publication number Publication date
DE4324931A1 (de) 1995-01-26
EP0635283A1 (fr) 1995-01-25
DE59407681D1 (de) 1999-03-04
ATE175882T1 (de) 1999-02-15

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