EP0302313B1 - Procédé et dispositif pour traiter des objets avec des solvants dans un récipient clos - Google Patents

Procédé et dispositif pour traiter des objets avec des solvants dans un récipient clos Download PDF

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Publication number
EP0302313B1
EP0302313B1 EP88111774A EP88111774A EP0302313B1 EP 0302313 B1 EP0302313 B1 EP 0302313B1 EP 88111774 A EP88111774 A EP 88111774A EP 88111774 A EP88111774 A EP 88111774A EP 0302313 B1 EP0302313 B1 EP 0302313B1
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EP
European Patent Office
Prior art keywords
container
solvent
treatment
water
immersion
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Expired - Lifetime
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EP88111774A
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German (de)
English (en)
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EP0302313A1 (fr
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Peter Weil
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Individual
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Individual
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Priority to AT88111774T priority Critical patent/ATE70315T1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44D—PAINTING OR ARTISTIC DRAWING, NOT OTHERWISE PROVIDED FOR; PRESERVING PAINTINGS; SURFACE TREATMENT TO OBTAIN SPECIAL ARTISTIC SURFACE EFFECTS OR FINISHES
    • B44D3/00—Accessories or implements for use in connection with painting or artistic drawing, not otherwise provided for; Methods or devices for colour determination, selection, or synthesis, e.g. use of colour tables
    • B44D3/24—Lamps for baking lacquers; Painters belts; Apparatus for dissolving dried paints, for heating paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44D—PAINTING OR ARTISTIC DRAWING, NOT OTHERWISE PROVIDED FOR; PRESERVING PAINTINGS; SURFACE TREATMENT TO OBTAIN SPECIAL ARTISTIC SURFACE EFFECTS OR FINISHES
    • B44D3/00—Accessories or implements for use in connection with painting or artistic drawing, not otherwise provided for; Methods or devices for colour determination, selection, or synthesis, e.g. use of colour tables
    • B44D3/16—Implements or apparatus for removing dry paint from surfaces, e.g. by scraping, by burning
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02806—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing only chlorine as halogen atom

Definitions

  • the invention relates to a method and a device for treating objects in a closed container with solvent, the objects to be treated being treated at least temporarily by immersion in solvent and then sprayed off in a solvent-free area of the container.
  • DE-A-33 00 666 discloses a washing process for small parts, in which the small parts are passed through solvents in treatment baskets in a closed container and are sprayed off above the solvent level. This process is used as a washing process and has some advantages, but it is not suitable for stripping or stripping objects.
  • the paint residues contain chlorine-containing solvents, which means expensive destruction. Only a limited use of additives, such as phenols, cresols or the like, is also possible for health and environmental reasons. With a degree of silting of the immersion baths of about 50%, the entire system must be destroyed or replaced. Due to the higher requirements for environmental compatibility, this known technology has been replaced by other processes.
  • pyrolysis it is known to carry out pyrolysis by means of higher temperatures.
  • pyrolysis which can take place at temperatures around 400 ° C.
  • no temperature-sensitive parts such as wood, plastic, hardened metals, thin sheets, light and non-ferrous metals, soldered parts, magnetized metals, etc.
  • halogen compounds can occur in the hot exhaust gases if, for example, polyvenyl chloride or chlorinated rubber is carbonized. These acidic gases can be neutralized in so-called after-washers.
  • the combustion produces highly toxic dioxins (Seveso), which can then be found in the wash water or can be released into the environment via the fireplace.
  • Paint stripping by burning is no longer possible today for environmental reasons, otherwise it can only be used to a limited extent, if at all.
  • hot stripping in hot alkali solutions or acids for example hot sulfuric acid
  • This treatment is dangerous, the baths are enriched with heavy metals, complexing agents, surfactants, so that there can ultimately be a pollution of the environment, especially of the waste water.
  • extremely aggressive, corrosive vapors also have a negative impact on the environment and personnel and must be recorded and neutralized in a complex manner.
  • used pickling liquids have to be destroyed in a cost-intensive manner. The amount of waste thus increases considerably and puts a strain on the sewage treatment plants due to large amounts of salt.
  • the object of the invention is to provide a solution with which the disadvantages described above are avoided not only when stripping paint, but also during other stripping treatment of surfaces, in particular also solvents in the coating materials can be completely removed and kept in the treatment process, and materials can be easily disposed of and can be treated in an environmentally friendly manner.
  • the process has considerable advantages over known processes.
  • a treatment agent mixture of solvent and an excess proportion of water azeotropic methylene chloride / water 98.5 to 1.5%, here for example 80 to 20%
  • the closed circuit avoids polluting emissions such as pollution of air, soil and water. Also, thermal removals of halogen coating materials become unnecessary, which means that it does not the formation of dioxides occurs, for example, in the pyrolysis of PVC.
  • the treatment in the boiling treatment agent mixture which in the example of methylene chloride boils with water at 38.1 ° C., shortens the treatment times many times over, so that the throughput of such a treatment is also reduced System increased or the size can be reduced accordingly, the amount of substances to be used can be kept correspondingly low.
  • Another advantage is that the materials that have to be removed from the surface of the objects to be treated can be removed in comparatively large pieces, which are then e.g. are recyclable. A load on the treatment liquids by foreign substances, such as resins or the like, is thereby avoided or reduced over a long period of time, so that rare regeneration phases can be maintained.
  • the invention provides that circulated water is used to remove the solvent from the system and from the coating or lacquer residues, at least some of this water having previously been used as part of the treatment agent mixture.
  • the water in the system can therefore be reused very often, which also leads to a very economical procedure.
  • One embodiment of the invention is that after the solvent has been completely removed from the system by boiling and recondensing, the parts in the treatment tank hosed and removed from the container and / or that the solvent-free residues are collected and recycled.
  • the invention also provides that the vapor phase of the solvent condenses in the upper region of the immersion tank and the condensate can be used as a spray. This has the advantage that the entire process, as far as the solvent is concerned, can be recycled, i.e. the risk of polluting the environment is avoided.
  • additives are added to the spraying agent.
  • These additives can be of very different types, they can be corrosives, chemicals for passivation, if with an acidic medium, for example in a medium containing formic acid, has been stripped, it can be oily and / or aqueous additives and the like. More.
  • the invention can also be used in the same way, e.g. for degreasing surfaces with other solvents or treatment mixtures in the liquid or vapor phase.
  • the expulsion of such solvents or treatment mixtures can then again be azeotropic, e.g. by boiling with water, for example: trichlorethylene with water (ratio 93.4% tri to 6.6% H2O) or tetrachloroethene with water in a ratio of 87.1% tetrachloroethene to 15.9% water, here the principle the system displacement by the higher boiling substance is exploited in a completely closed procedure.
  • the environmentally harmful azeotrope component should be driven out in the system by the less or not at all polluting substance (here essentially H2O).
  • the procedure according to the invention has additional advantages. For example the following: Low operating costs, since only the low heating costs, in order to work with warm stripping agents and later to distill extractively, require energy. Thermal treatments require temperatures of approx. 400 ° C compared to 38.1 ° C or 100 °.
  • stripping agents are only present in the system as an intermediate stage, as in most extractive processes, and are removed from them after the stripping process, they do not cause any additional waste problems. (Cold paint removers with a content of approx. 50% paint are often destroyed due to silting up, i.e. doubling and additional pollution of the waste with environmentally harmful additives).
  • the dampened aggressiveness enables small surface changes compared to many raw materials by using inhibitors in the acidic as well as in the alkaline range. Strongly caustic processes are often used to remove extremely resistant layers from sensitive base materials. (Hot concentrated sulfuric acid, hot caustic soda, etc.). This doesn't just mean Surface changes, but also complex neutralization in the aftertreatment (over-salting of the waste water).
  • the invention also provides a system with an immersion tank which can be at least partially filled with a treatment agent mixture and which is equipped with a heating device in its lower area and with a cooling device in the area of the cover provided above, the cooling device including a condensate collecting channel Drain lines is assigned, this system being characterized in that the heating device as a water evaporation device formed, a drain is provided in the lower region of the immersion tank and at least one collecting tank for solvents and one collecting tank for water is assigned to the immersion tank, a diving basket and / or on its underside being used in the immersion tank to remove the coating or varnish residues from the immersion tank additional perforated plate is provided.
  • GB-A-870 970 shows a system with a water cover over a solvent reservoir, which is suitable for treating articles in a pass.
  • US-A-2 310 569 shows a system with which it is possible to condense back solvent in the vapor phase, this system also having a lower heater.
  • the cooling device in the area of the upper edge is able to condense the solvent vapors, so the solvent can be removed from the container.
  • a further heating of the water via the heating device then ensures the evaporation of the water, here too the condensate or cooling device in the head region of the container can be used to return the water to other parts of the system, which means that before opening the lid, all evaporable components can be removed from the container.
  • the cooling device in the head area of the immersion tank also has the task of forming a type of vapor barrier when the tank is open, but if solvent residues, for whatever reason, should remain in the open tank, their vapors can then be condensed without causing it to environmental pollution.
  • a spraying device can be installed in a stationary manner, but it can also be a spraying lance or the like which can be operated by hand, of course both options can also be provided at the same time.
  • the gas space is to be understood as both the space above a liquid level and the total space of the container when the treatment agent mixture has been pumped out.
  • the invention has the particular advantage of the completely closed mode of operation.
  • at least one collecting container for solvents, one collecting container for water and one collecting container for a further treatment agent, such as a neutralizing agent or the like are assigned to the immersion container.
  • a further treatment agent such as a neutralizing agent or the like
  • At least one of the collection containers for solvents can also be used as a collection container for the treatment agent mixture, i.e. e.g. for the mixture of methylene chloride with an excess of water based on the azeotropic mixture.
  • the immersion tank can be provided with an activated carbon filter and / or a pressure compensation tank.
  • These system elements have the task of providing gas volume compensation when the container is closed and after flooding with the treatment agent mixture when the heating device begins to heat. The portion of the gas volume expanding over the treatment agent mixture is released into the environment via the activated carbon filter by increasing the volume compared to the gas space volume of the immersion tank, or it acts on the pressure compensation tank.
  • One embodiment of the invention consists in that a collecting container for a further treatment agent, such as a neutralizing agent or the like, an activated carbon filter and / or a pressure compensation container is assigned to the immersion container.
  • a further treatment agent such as a neutralizing agent or the like
  • an activated carbon filter and / or a pressure compensation container is assigned to the immersion container.
  • the system generally designated 1 for the treatment, for example for stripping or stripping, of objects 2 consists essentially of a dip tank 3, which can be closed by a removable cover 4 on the top. Through the opening released by the lid 4, the immersion container 3 is loaded with the objects 2 to be treated, which are arranged, for example, in an immersed basket 5.
  • the immersion tank 3 is provided in the lower area with a heating device 6, in the upper area near the cover 4 with cooling coils 7, which are equipped with a condensate channel 8 underneath.
  • Storage tanks are provided for receiving treatment liquid and / or neutralizing agent and / or water or the like, such as the treating agent tank 9, the condensate / water tank 10 and the neutralizing agent tank 11, each of which is shown in the figure by additional tanks 9a, 9b or 10a and 11a are added to show that the type and size of the tanks are not important.
  • a relief line 12 is provided, which leads to an activated carbon plant 13 and to a pressure compensation tank 14. Via the activated carbon system 13, a gas volume can be released to the environment via the valve 15, which gas volume is formed by thermal expansion when heated.
  • the immersion container 3 is approximately half filled with liquid so that the container is divided into a liquid region 16 and a gas space 17.
  • spray devices are provided, e.g. a permanently installed spraying system 18 and a manual spraying system 19, the specific design of which is not important.
  • the system works as follows: If the container is empty, it can be filled with the latter for the treatment of the objects 2. First, the cover 4 is removed and the cooling runs over the cooling device 7. After equipping the immersion basket 5, which can be provided with an additional perforated plate 5a on one of its undersides, for example, it is introduced into the immersion container 3 from above. Now the lid is closed and, for example, a mixture of methylene chloride and alcohols and other solvents, acids or alkali, such as, for example, armines or surfactants or the like, and water is introduced in an over-azeotropic ratio from the tank or tanks 9 or 9a, 9b.
  • the tanks 9, 9a, 9b can be arranged higher in the direction of gravity than the highest filling level of the container 3, so that an additional pumping is unnecessary when filling, but a complete pumping out of the mixture can be ensured when emptying.
  • the heating device After flooding, the heating device is turned on and the treatment agent mixture is heated, a mixture of methylene chloride / water azeotrope boiling at 38.1 ° C. in a ratio of 98.5 to 1.5%. Boiling or bubbling the liquid accelerates the reaction, the treatment time of the parts 2 to be treated can thus e.g. compared to a cold stripping process can be shortened by a multiple, approximately 10 to 20 times, which means a 10 to 20 times higher throughput of the system.
  • the gas mixture expanding in the gas space 17 is fed via the line 12, for example to the activated carbon filter system 13, and can be released into the environment via the valve 15.
  • a vapor of solvent and water which then forms in the gas space 17 is condensed on the cooling coils 6 and collected via the condensate collecting channel 8 and, for example via a bypass line 20, is fed directly back to the immersion container 3.
  • the heating is switched off.
  • methylene chloride as solvent, it settles down below after a short time, while the water floats up as a lighter medium.
  • the methylene chloride can now be pumped back into or into one of the containers 9 to 9b, and a water fraction is left in the immersion container 3.
  • the extraction phase begins, i.e. the heating is switched on again.
  • the methylene / water mixture boils again azeotropically at 38.1 ° C.
  • the gas phase is condensed again on the cooling coils and is now fed to the storage tank 9 via line 21. If the temperature rises above 38.1 ° C, the operator finds that all methylene chloride has been distilled out. Between this temperature and the boiling point of water there are further azeotropes of the other additives, such as alcohols, formic or acetic acids, esters and the like. Like. These can then be distilled out accordingly.
  • the lid can be removed. Solvents are now completely removed from the immersion container 3, there are only parts of lacquer or paint or plastics or other detached coating materials and possibly water in the container.
  • the parts are hosed down by the stationary or the hand-operated spraying systems 18 and 19, in such a way that the coatings, which generally peel off over a large area, collect in the lower perforated plate 5a.
  • additives may also be added to the water to be treated, such as anti-corrosion agents or the like. This also saves an external spraying place by spraying in the immersion tank.
  • the water-wet residues on the perforated plate can be dewatered via filter presses or the like and can be reused. With the appropriate procedure, the hosed and removed parts are still comparatively warm, so that they dry very quickly, which additionally reduces corrosion.
  • a solvent vapor treatment in the steam space 17 can also be carried out simultaneously, e.g. of objects that are not suitable for immersion treatment, e.g. Light metals and their alloys, non-ferrous metals, wood, plastics u. This procedure can e.g. also used for incorrectly painted parts from electronics, from aircraft construction, from automobile production, for example for light alloy high-speed rims. Like. more.
  • the system can work completely closed, a certain volume of gas is discharged in the upward process via the activated carbon filter system 13, it is the only emission to the environment, but this volume can also be collected in a pressure expansion tank 14, then the system is pressurized to a certain extent operated towards the environment.
  • degreasing processes or other treatment processes can also be carried out in the system, depending entirely on the liquid mixtures used or their over-azeotropic compositions.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Treatment Of Fiber Materials (AREA)

Claims (9)

  1. Procédé pour traiter des objets dans un récipient clos avec des solvants, les objets à traiter étant traités au moins temporairement par immersion dans les solvants et étant ensuite aspergés dans une région du récipient qui ne comprend pas de solvant, caractérisé en ce que l'on utilise le procédé de dévernissage et d'enlèvement de revêtements d'objets avec au moins les étapes de procédé additionnelles suivantes:
    a) on utilise en tant qu'agent de traitement et après fermeture du récipient de traitement un mélange comprenant au moins une fraction principale de solvant, telle que du chlorure de méthylène, avec une fraction complémentaire d'eau pour obtenir un mélange azéotrope,
    b) le mélange d'agent de traitement est chauffé à la température d'ébullition du mélange,
    c) quand la durée de traitement est terminée, le solvant qui se dépose et éventuellement se condense est retiré du récipient de traitement,
    d) l'eau est chauffée et évaporée dans le récipient de traitement,
    e) le solvant se trouvant sur ou dans les déchets de revêtement et sur les objets traités étant distillé et éliminé du système de façon azéotrope avec de l'eau avant l'ouverture du récipient.
  2. Procédés selon la revendication 1, caractérisé en ce que pour éliminer le solvant du système et des déchets de revêtement ou de laque, on utilise l'eau envoyée dans le circuit, une partie au moins de cette eau ayant été préalablement utilisée en tant que composant du mélange d'agent de traitement.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'après une élimination totale du solvant hors du système par ébullition et recondensation, on asperge les pièces dans le récipient de traitement et on les retire de ce récipient.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on rassemble les déchets ne contenant pas de solvant et notamment on les réutilise.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que seulement une partie du récipient de traitement est remplie de solvant et le niveau de remplissage du solvant est maintenu à une certaine distance de serpentins de refroidissement et de condensation prévus dans la région du couvercle du récipient.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le mélange d'agent de traitement est utilisé également comme agent d'aspersion dans l'enceinte à gaz du récipient de traitement.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on ajoute au mélange d'agents de traitement des additifs en vue de la passivation ou de la protection contre la corrosion.
  8. Installation pour la mise en oeuvre du procédé selon l'une des revendications précédentes, comprenant au moins un récipient d'immersion (3) pouvant être rempli au moins en partie avec un mélange d'agent de traitement, qui est équipé d'un dispositif de chauffage (6) dans sa région inférieure et d'un dispositif de refroidissement (7) dans la région du couvercle (4) prévu à sa partie supérieure, une rigole de rassemblement de condensat (8) comprenant des conduites d'évacuation étant associée au dispositif de refroidissement (7),
       caractérisée par le fait que le dispositif de chauffage (6) est constitué sous forme d'un dispositif de vaporisation d'eau, qu'il est prévu dans la région inférieure du récipient d'immersion (3) une conduite d'évacuation et qu'il est associé au récipient d'immersion (3) au moins un récipient collecteur (9) pour le solvant et un récipient collecteur (10) pour l'eau, une corbeille d'immersion (5) et/ou une tôle perforée additionnelle (5a) sur son côté inférieur étant prévues dans le récipient d'immersion (3) pour retirer les déchets de revêtement ou de laque hors de ce récipient.
  9. Installation selon la revendication 8, caractérisée en ce qu'il est associé au récipient d'immersion (3) un récipient collecteur (11) pour un autre agent de traitement tel qu'un agent de neutralisation ou analogue, un filtre à carbone actif (13) et/ou un récipient d'égalisation de pression (14).
EP88111774A 1987-08-01 1988-07-21 Procédé et dispositif pour traiter des objets avec des solvants dans un récipient clos Expired - Lifetime EP0302313B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88111774T ATE70315T1 (de) 1987-08-01 1988-07-21 Verfahren und vorrichtung zum behandeln von gegenstaenden in einem geschlossenen behaelter mit loesungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3725565 1987-08-01
DE3725565A DE3725565A1 (de) 1987-08-01 1987-08-01 Verfahren und anlage zum entlacken von gegenstaenden mit einem tauchbehaelter mit loesungsmittel

Publications (2)

Publication Number Publication Date
EP0302313A1 EP0302313A1 (fr) 1989-02-08
EP0302313B1 true EP0302313B1 (fr) 1991-12-11

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EP88111774A Expired - Lifetime EP0302313B1 (fr) 1987-08-01 1988-07-21 Procédé et dispositif pour traiter des objets avec des solvants dans un récipient clos

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Country Link
US (1) US5011542A (fr)
EP (1) EP0302313B1 (fr)
JP (1) JPH02500178A (fr)
KR (1) KR950014078B1 (fr)
AT (1) ATE70315T1 (fr)
BR (1) BR8807154A (fr)
DE (2) DE3725565A1 (fr)
ES (1) ES2027351T3 (fr)
GR (1) GR3003993T3 (fr)
WO (1) WO1989001057A1 (fr)

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GR3003993T3 (fr) 1993-03-16
DE3725565A1 (de) 1989-02-16
KR950014078B1 (ko) 1995-11-21
KR890701799A (ko) 1989-12-21
WO1989001057A1 (fr) 1989-02-09
EP0302313A1 (fr) 1989-02-08
US5011542A (en) 1991-04-30
DE3866820D1 (de) 1992-01-23
ES2027351T3 (es) 1992-06-01
BR8807154A (pt) 1989-10-17
JPH02500178A (ja) 1990-01-25
ATE70315T1 (de) 1991-12-15

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