EP0424865B1 - Enlèvement des dioxines et furannes - Google Patents

Enlèvement des dioxines et furannes Download PDF

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Publication number
EP0424865B1
EP0424865B1 EP90120277A EP90120277A EP0424865B1 EP 0424865 B1 EP0424865 B1 EP 0424865B1 EP 90120277 A EP90120277 A EP 90120277A EP 90120277 A EP90120277 A EP 90120277A EP 0424865 B1 EP0424865 B1 EP 0424865B1
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EP
European Patent Office
Prior art keywords
process according
dioxins
furans
layers adjacent
contaminated
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 - Lifetime
Application number
EP90120277A
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German (de)
English (en)
Other versions
EP0424865A3 (en
EP0424865A2 (fr
Inventor
Alfred Esser
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.)
Sprintsystem Gesellschaft fur Sanierungstech GmbH
Original Assignee
Sprintsystem Gesellschaft fur Sanierungstechnik Organisation und Weiterbildung & Co GmbH
Sprintsystem Gesellschaft fur Sanierungstechnik Organisation und Weiterbildung & Co GmbH
SPRINTSYSTEM GmbH
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
Application filed by Sprintsystem Gesellschaft fur Sanierungstechnik Organisation und Weiterbildung & Co GmbH, Sprintsystem Gesellschaft fur Sanierungstechnik Organisation und Weiterbildung & Co GmbH, SPRINTSYSTEM GmbH filed Critical Sprintsystem Gesellschaft fur Sanierungstechnik Organisation und Weiterbildung & Co GmbH
Publication of EP0424865A2 publication Critical patent/EP0424865A2/fr
Publication of EP0424865A3 publication Critical patent/EP0424865A3/de
Application granted granted Critical
Publication of EP0424865B1 publication Critical patent/EP0424865B1/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
    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • A62D3/176—Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B15/00—Preventing escape of dirt or fumes from the area where they are produced; Collecting or removing dirt or fumes from that area
    • B08B15/02—Preventing escape of dirt or fumes from the area where they are produced; Collecting or removing dirt or fumes from that area using chambers or hoods covering the area
    • 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

Definitions

  • the present invention relates to a method for removing dioxins and / or furans from layers near the surface, in particular from surfaces contaminated by fire damage.
  • wet cleaning high-pressure hot washing with the addition of a wetting agent
  • treatment of the surfaces with solvents such as toluene can be considered according to the prior art. If further cleaning is required, unsatisfactory results with manual wet cleaning are not available, especially for uncoated surfaces, for example metal surfaces.
  • EP-A 0 257 170 discloses a process for the decontamination of surfaces and liquids, in which UV radiation, if appropriate in the presence of hydrogen atoms, when using special reagents for reaction with the dioxins and / or furans, namely wetting agents, alcoholates and / or Radical formers, halogenated and polyhalogenated organic compounds are broken down.
  • WO 79/00835 describes the dehalogenation of halogenated compounds in solution by means of UV radiation under the action of oxidizing gases such as oxygen, air or ozone as prior art.
  • oxidizing gases such as oxygen, air or ozone
  • U.S. Patent 3,977,952 uses UV radiation in the presence of hydrogen gas in the absence of oxidizing agents.
  • the object of the present invention is to remove dioxins and / or furans from layers near the surface, in particular in the event of fire.
  • dioxins and / or furans are desirable, for example when decontaminating control cabinets or other machine systems, to keep them in operation during the renovation.
  • the object according to the invention is achieved by a method for removing dioxins and / or furans from layers near the surface, the contaminated, solid surfaces optionally being suctioned off dry first, the suction material on one Substrate adsorbed and disposed of, characterized in that the contaminated layers near the surface are isolated from the ambient room air and by passing air and / or an exchange gas over the layers, a gas flow is generated at the layers near the surface, which before or after painting over the layers near the surface is passed over a surface-active adsorbent and the gas stream is exposed to ionizing radiation.
  • near-surface layer within the meaning of the invention naturally includes the actual solid surface and in particular the visible solid surface.
  • the contaminated layers near the surface can be isolated from the ambient air, for example by partitioning them off with a film, it being possible to generate a gas stream on the contaminated surface which is isolated from the surrounding ambient air.
  • Devices for sucking in room air from dioxin-contaminated rooms are known per se.
  • the ambient air is adsorbed on a substrate, in particular through a filter system consisting of a prefilter and a special activated carbon filter, and then passed through an ionization stage in which existing gaseous components or aerosols can be split.
  • the method according to the invention is particularly suitable for near-surface layers such as floors, wall surfaces, ceilings, building rubble, scrap, soil, means of transport, in particular vehicles or ships, technical systems, electronic devices, machines, transport containers and / or control cabinets.
  • Switching off the devices which are contaminated by dioxins and / or furans is not absolutely necessary during the implementation of the method according to the invention, since there is no wet cleaning stage is necessary, which was previously considered necessary in the prior art.
  • the typical fire smell that practically always occurs after fire damage is also eliminated.
  • the treatment of building rubble can be carried out, for example, in such a way that it is exposed to the gas flow from top to bottom or vice versa on a perforated, air-permeable surface and, if appropriate, is exposed to radiation with artificial UV radiation.
  • the method is carried out in a closed system. This can be done, for example, by first isolating the contaminated surface from the room air in a control cabinet after opening the doors by inserting a partition with a lock, for example using a cover film, and creating a closed system.
  • An air filter device known per se is flanged to this system with the aid of air channels or hoses and a gas stream is cyclically circulated in the system with the aid of a blower until the content of dioxins and / or furans is reduced to the desired values.
  • the gas flow sweeps over the sometimes difficult to access surfaces of the electrical components of the control cabinet.
  • FIG. 1 shows a partial view of a preferred embodiment of the present invention.
  • the contaminated wall surface (1) is isolated from the ambient air by a sealing film (2).
  • the UV lamp (4), (4 ′) and (4 ⁇ ) as well as tubular air inlet openings (5) and air intake openings (6), to which a filter unit (7) is located are located in the cavity (3) thus created.
  • the cavity (3) between the wall surface (1) and the film is laterally isolated from the surrounding room air by sealing measures - not shown. After contact with the filter, the gas flow is subjected to ionization and circulated until the decontamination gives acceptable values.
  • the gas flow direction can also be set against the direction of the arrow.
  • Fig. 2 shows a perspective view along the viewing angle (II) of Fig. 1 and shows that practically the entire wall surface is irradiated by the UV lamps (4), (4 ') and (4 ⁇ ).
  • the separation devices (8) and (9) With the help of the separation devices (8) and (9) a system is created that is sealed off from the ambient air.
  • FIG 3 shows a preferred embodiment of the filter device (7) to be used according to the invention in a closed system using the example of a control cabinet (10).
  • a gas flow is generated along the direction of the arrow, which reaches the ionization stage (14) after contact with the prefilter (12) and then the main filter (13).
  • the gas stream is then passed through the post-filter (15).
  • the method according to the invention is carried out in a closed system, the gas stream is circulated until the contamination of dioxin and / or furans is reduced to acceptable values.
  • FIG. 4 shows a special embodiment of a non-closed system for removing dioxins and / or furans according to the present invention.
  • the fan (11) generates a gas stream which is passed over the contaminated surfaces and then, after painting over the contaminated surface, reaches the filter unit (7) (not shown), the gas stream passing through a pre-filter (12), a main filter (13) and a subsequent ionization stage (14) is guided. This is followed by a post-filter stage (15).
  • the pressure and / or the gas flow rate in the incomplete system can be set as desired by varying the suction power of the blower (16) in conjunction with the blower (11).
  • One way of creating a closed system is for the gas flow to be introduced and carried out through the ventilation slots in a closed control cabinet.
  • immovable objects such as machines
  • Foreclosure can be done, for example, by placing a tent over the object to be decontaminated, under which the objects to be treated and any equipment required are to be placed. It is possible to remove contaminations inside the machines or systems without the need for a wet treatment which is hazardous to corrosion. It is also possible to create stationary facilities into which objects to be decontaminated are placed.
  • the pressure prevailing in the system can be freely selected. This can therefore be lower, equal or higher than the external air pressure and, of course, can also be varied once or several times during the treatment time of the contaminated surface.
  • the gas flow rate In addition to the pressure, it is also possible to set the gas flow rate.
  • An increased gas flow rate causes a faster removal of the dioxins and / or furans from the contaminated surfaces to be treated.
  • the influence of the temperature of the gas stream and the relative humidity is also of some importance. It is readily possible to carry out the treatment of the surfaces at temperatures which are increased or decreased compared to room temperature.
  • the increase in temperature with a simultaneous lowering of the air humidity leads, in particular if the layers near the surface are wetted beforehand due to the good ones Aerosol binding of the dioxins and / or furans so that they are highlighted from deeper layers and brought to the surface. This allows the contamination to be removed beyond the visible surface in the layers near the surface.
  • the dioxins and / or furans to be broken down then get into the gas stream by evaporation on the surface.
  • activated carbon is particularly preferably used as the surface-active adsorbent.
  • filter systems which, for example, consist of a pre-filter, a chemical main filter - in particular specially doped activated carbon of high weight - and a post-filter. While the pre-filter is intended to trap visible particles in the air, the chemical filter reacts with the dioxins or furans and binds these substances.
  • activated carbon Variosorb R A is suitable for this.
  • the post-filter filters out residual particles and keeps the cleaning stage inside and the blower clean.
  • the ionizing radiation acting on the gas stream can be generated by methods known per se. Vacuum UV tubes are particularly suitable.
  • the task of the ionization stage in the remediation is to neutralize gas molecules by micro-oxidation by producing energy-charged atoms, for example oxygen atoms, to accelerate the removal and / or the chemical conversion of the dioxins and / or furans into harmless compounds and thus also to increase the lifespan of the extend chemical filter.
  • energy-charged atoms for example oxygen atoms
  • the remaining filters can be disposed of in a known manner by catalytic combustion.
  • Another embodiment of the present invention consists in exposing the near-surface layers to ultraviolet radiation before, during or after the treatment by the gas stream. From “reports” 5/85, the photo-degradation of polychlorinated dibenzo-p-dioxins on a laboratory scale is known in principle, but no degradation could be detected when irradiating 2,3,7,8-TCDD suspended in crystalline form in distilled water.
  • liquid, non-reactive media it can be advantageous to apply liquid, non-reactive media to the layers near the surface before and / or during the irradiation in the region of room temperature.
  • a further embodiment of the present invention is characterized in that the applied non-reactive medium is selected from solvents or preferably non-solvents for dioxins and furans.
  • the applied non-reactive medium is selected from solvents or preferably non-solvents for dioxins and furans.
  • liquid aliphatic, aromatic-aliphatic and / or aromatic hydrocarbons, halogenated hydrocarbons, glycols, ethers, glycol ethers, ketones and / or esters can be used as solvents in the region of room temperature will.
  • a strongly absorbent substrate there is the possibility that the dioxins and / or furans diffuse into deeper, unreachable layers.
  • the liquid, non-reactive media can, for example, be sprayed or painted onto the surfaces before the treatment. Suitable objects can also be immersed directly in the media. In addition, the liquid, non-reactive media can be added to the gas stream.
  • dioxins and / or furans can be carried along, for example, as a suspension, solution or aerosol and exposed to the radiation on the surface.
  • low-boiling solvents or non-solvents such as alcohols, in particular methanol, ethanol, propanols and / or butanols can also be used.
  • a wetting agent can also be added to the aforementioned media.
  • the task of the wetting agent is, according to the invention, to introduce the solvent and / or the non-solvent for dioxins and furans into the contaminated areas.
  • UV radiation in the range from 200 to 280 nm, ie UV-C radiation, is preferably used.
  • a decontamination system consisting of a filter unit (7), a vacuum UV radiation source (14) and a blower (11) was flanged onto it via two air channels (5) and (6).
  • Variosorb R A activated carbon was used as filter material (13) in an amount of about 8 kg, 5 IRE tubes in the blow-out stream as ionization stage and a radial fan with a pump capacity of about 1000 m3 / h.
  • the contamination determined by wiping test was reduced from 104 ng / m2 of polychlorinated dibenzofurans to 9 ng / m2. This corresponds to an efficiency of 91%.
  • the TCDD equivalents were 2.6 ng / m2 before exposure and 0.22 ng / m2 after treatment. Based on the TCDD equivalents, this corresponds to an efficiency of 91%.
  • the size of the wall area was 8.2 m2.
  • a black plastic film was used as the cover film (2) to enable further work in the contaminated room.
  • the contamination determined by means of a wipe test was reduced from 80 ng / m2 of polychlorinated dibenzofurans to 2.8 ng / m2. This corresponds to an efficiency of 96%.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emergency Management (AREA)
  • Business, Economics & Management (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Saccharide Compounds (AREA)

Claims (16)

  1. Procédé d'enlèvement de dioxines et/ou de furannes de couches proches d'une surface, selon lequel on soumet éventuellement tout d'abord à une aspiration à sec les surfaces solides contaminées, on provoque l'adsorption sur un substrat de la matière ainsi aspirée et l'on élimine cette matière, caractérisé en ce que les couches proches de la surface et contaminées sont isolées de l'air ambiant, et, en faisant passer en balayage de l'air et/ou un gaz de remplacement au-dessus des couches, on produit sur les couches voisines de la surface un courant gazeux qui, avant ou après le balayage des couches proches de la surface, est dirigé au-dessus d'un agent tensio-actif d'adsorption et est soumis à un rayonnement ionisant.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on traite des couches, voisines de la surface, de planchers, de surfaces de cloisons et parois, de toits, de gravats, de ferrailles, de sols de terrains, de moyens de transport, notamment des véhicules automobiles ou des bateaux, d'installations techniques, d'appareils électroniques, de machines, de récipients de transport ou conteneurs, et/ou d'armoires électriques de commande et/ou de distribution.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les couches proches d'une surface sont exposées au traitement à l'intérieur d'un système clos.
  4. Procédé selon la revendication 3, caractérisé en ce que, par rapport à la pression de l'air extérieur, il y a ajustement à une pression de gaz réduite ou plus élevée.
  5. Procédé selon la revendication 4 caractérisé en ce que, pendant la durée du traitement, la pression du gaz du système est modifiée une ou plusieurs fois.
  6. Procédé selon les revendication 1 à 5, caractérisé en ce que, pendant le traitement des couches voisines de la surface, la vitesse d'écoulement du gaz est soumise à variation(s).
  7. Procédé selon les revendication 1 à 6, caractérisé en ce qu'on utilise du charbon actif comme agent tensio-actif d'adsorption.
  8. Procédé selon les revendication 1 à 7, caractérisé en ce que le rayonnement ionisant est produit à l'aide de tubes à ultra-violet sous vide.
  9. Procédé selon les revendication 1 à 8, caractérisé en ce que, avant, pendant ou après le traitement par le courant gazeux, les couches voisines de la surface sont en outre soumises à un rayonnement ultra-violet artificiel.
  10. Procédé selon la revendication 9, caractérisé en ce que les couches voisines de la surface sont soumises à un rayonnement ultra-violet dont les longueurs d'ondes se situent entre 200 et 280 nm.
  11. Procédé selon les revendications 9 ou 10, caractérisé en ce que, pendant le rayonnement, la température de la surface à traiter est élevée par rapport à la température ambiante et/ou l'humidité est diminuée.
  12. Procédé selon les revendications 9 à 11, caractérisé en ce que sur les couches voisines de la surface, des milieux non réactifs liquides à la température ambiante sont appliqués avant et/ou pendant le rayonnement.
  13. Procédé selon la revendication 12, caractérisé en ce que sont appliqués des milieux qui sont choisis parmi des solvants et/ou des non-solvants des dioxines et furannes.
  14. Procédé selon la revendication 13, caractérisé en ce qu'on utilise comme solvant des hydrocarbures aliphatiques, aromatiques-aliphatiques et/ou aromatiques, des hydrocarbures halogénés, des glycols, des éthers, des éthers de glycol(s), des cétones et/ou des esters, liquides au voisinage de la température ambiante.
  15. Procédé selon la revendication 13, caractérisé en ce qu'on utilise comme non-solvant de l'eau, des alcools, en particulier le méthanol, l'éthanol des propanols et/ou des butanols.
  16. Procédé selon les revendications 13 à 14, caractérisé en ce qu'on ajoute un agent de mouillage au milieu liquide.
EP90120277A 1989-10-25 1990-10-23 Enlèvement des dioxines et furannes Expired - Lifetime EP0424865B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3935534 1989-10-25
DE3935534A DE3935534C1 (fr) 1989-10-25 1989-10-25

Publications (3)

Publication Number Publication Date
EP0424865A2 EP0424865A2 (fr) 1991-05-02
EP0424865A3 EP0424865A3 (en) 1991-11-13
EP0424865B1 true EP0424865B1 (fr) 1994-12-28

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EP90120277A Expired - Lifetime EP0424865B1 (fr) 1989-10-25 1990-10-23 Enlèvement des dioxines et furannes

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EP (1) EP0424865B1 (fr)
AT (1) ATE116142T1 (fr)
DE (2) DE3935534C1 (fr)
DK (1) DK0424865T3 (fr)
ES (1) ES2068309T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393394A (en) * 1992-08-18 1995-02-28 Kabushiki Kaisha Toshiba Method and apparatus for decomposing organic halogen-containing compound
DE4437345A1 (de) * 1994-04-22 1995-10-26 Svt Brandschutz Vertriebsgesel Verfahren zur Dekontamination von verunreinigten porösen Werkstoffen und eine Anlage zur Durchführung des Verfahrens
DE19707914A1 (de) * 1997-02-27 1998-09-03 Babcock Anlagen Gmbh Verfahren und Vorrichtung zum Behandeln von Asche
CN115646442A (zh) * 2022-10-24 2023-01-31 苏州市吴中区固体废弃物处理有限公司 一种利用生活垃圾焚烧飞灰制备吸附剂的方法及吸附剂

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144152A (en) * 1978-03-27 1979-03-13 Atlantic Research Corporation Dehalogenation of halogenated compounds
DE3010130A1 (de) * 1980-03-15 1981-09-24 Walter 7460 Balingen Link Verfahren und geraet zum reinigen von gegenstaenden und raeumen
US4287038A (en) * 1980-05-08 1981-09-01 Uop Inc. Purification of chlorophenolic derived compounds
EP0257170B1 (fr) * 1986-08-29 1990-10-24 SEA MARCONI TECHNOLOGIES S.p.a. Procédé pour la décomposition chimique rapide de composés organiques halogénés et polyhalogénés, par exemple les biphényles polychlorés, les dibenzofuranes polychlorés et les dibenzodioxins polychlorés, et de la désintoxication des surfaces ou fluides
DE8704276U1 (fr) * 1987-03-21 1987-08-06 Harress, Heinz Michael, Dr., 8856 Harburg, De

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Publication number Publication date
DK0424865T3 (da) 1995-04-03
EP0424865A3 (en) 1991-11-13
ATE116142T1 (de) 1995-01-15
EP0424865A2 (fr) 1991-05-02
ES2068309T3 (es) 1995-04-16
DE59008131D1 (de) 1995-02-09
DE3935534C1 (fr) 1991-04-18

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