EP0238517B1 - Method and apparatus for rinsing surfaces with non-aqueous liquids - Google Patents
Method and apparatus for rinsing surfaces with non-aqueous liquids Download PDFInfo
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- EP0238517B1 EP0238517B1 EP86905186A EP86905186A EP0238517B1 EP 0238517 B1 EP0238517 B1 EP 0238517B1 EP 86905186 A EP86905186 A EP 86905186A EP 86905186 A EP86905186 A EP 86905186A EP 0238517 B1 EP0238517 B1 EP 0238517B1
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- rinsing
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S134/00—Cleaning and liquid contact with solids
- Y10S134/902—Semiconductor wafer
Definitions
- the present invention relates to a process for rinsing surfaces without the use of water, and to an installation for implementing this process.
- this type of method has at least two drawbacks, namely that it leads to the formation of large quantities of polluted water which are incompatible with the requirements, currently increasingly severe, of environmental protection, and that aqueous solutions thus removed from surfaces, even if they can be recovered, are generally degraded and unusable.
- azeotropes that is to say by solubilization of water in the solvent (7% of water in the azeotrope trichlorethylene-water); in this case there is little or no oxidation of the surfaces, but the problem of stains is not resolved however.
- Patent application FR-A-2 213 788 describes a process for removing water from a surface by making it hydrophobic, by using a bath comprising chlorinated or chlorofluorinated solvents immiscible with water. water, mixed with water-miscible solvents such as isopropanol, generally containing surfactants of the type described in US Pat. No. 3,397,150 and forming an azeotropic mixture with water.
- the liquid to be removed from a surface is for example a galvanic solution
- the fact that there is use of baths of solvent liquids and formation of azeotropic mixtures between the two liquid phases implies an extraction phenomenon liquid-liquid and therefore an alteration of the galvanic bath, which can no longer be reused as it is.
- the aim of this invention is to obviate the drawbacks of the known methods for rinsing surfaces, by providing a process which does not require the use of water, nor of surfactants, nor of baths of solvents capable of favor the formation of azeotropic mixtures or lead to liquid-liquid extractions, and which makes it possible to maintain the treated surfaces hydrophilic and to recover the aqueous liquid eliminated without altering it.
- the method according to the invention aimed at achieving the above object has the characteristics mentioned in claim 1.
- the non-solvent liquid intended to form an emulsion with the aqueous liquid to be eliminated is chosen from completely fluorinated organic compounds.
- Another object of this invention consists of an installation for implementing the method according to the invention, which has the characteristics defined in claim 3.
- the appended drawing illustrates schematically and by way of example an embodiment of an installation according to the invention for rinsing surfaces.
- any known technique can be used.
- a container containing the LFI can be used and in which the parts are immersed. These can be placed in bulk in baskets or drums, mounted on racks provided for this purpose, or suspended in the case of larger pieces, or held in the LFI by any type of support, or also in the case of a continuous technique in the form of a passage in strip, wire, film, etc.
- the emulsion is preferably obtained by application of ultrasound, for example at frequencies generally between 20 and 80 kHz, or by more or less energetic agitation and vibration of the parts to be treated immersed either mechanically transmitted by an external source, or induced electromagnetically inside the parts, or by vibration of the container itself and transmission to the parts submerged by the liquid.
- ultrasound for example at frequencies generally between 20 and 80 kHz, or by more or less energetic agitation and vibration of the parts to be treated immersed either mechanically transmitted by an external source, or induced electromagnetically inside the parts, or by vibration of the container itself and transmission to the parts submerged by the liquid.
- spraying and spraying techniques can be used at higher or lower pressures.
- the inert non-solvent liquid used in the process according to the invention is preferably a completely fluorinated organic compound, for example of the "Fluorinert” type (from the company 3M).
- fluorinert a completely fluorinated organic compound
- These compounds derived from common organic compounds by replacement of all the hydrogen atoms, by fluorine atoms, therefore contain neither hydrogen nor chlorine. They are non-polar and have practically no solvent action, in particular with regard to water and the constituents of industrial aqueous liquids such as galvanic baths. They are colorless, odorless, slightly toxic and non-flammable, but above all have high thermal stability and are chemically inert.
- LFI compounds are therefore completely different in their properties from the chlorofluorinated solvents usually used as solvents, degreasing and drying agents, etc.
- exceptional chemical inertness of LFIs means that they do not make the treated surfaces hydrophobic, do not contaminate or modify in any way the aqueous solutions that they emulsify, these can therefore be reused directly upstream of the manufacturing process, after demulsification.
- Some stable fluorosurfactants can dissolve to some extent in LFIs. Consequently, and although this is not generally necessary, it may in certain cases be useful to incorporate it into the LFI, provided of course that they do not risk rendering the surfaces hydrophobic, and, in order to increase the effectiveness and speed of rinsing, especially when using the spraying / sprinkling technique.
- the same effect as above can also be obtained by incorporating the stable fluorosurfactant into the aqueous liquid to be removed.
- completely fluorinated organic liquids does not however exclude that other partially fluorinated products, for example of the "Freon 113" type, can also be used, in certain cases and essentially for economic reasons and / or when the quality requirements of the surfaces are lower. In this case, and to compensate for the lower emulsifying power, it is recommended to add a surfactant of the aforementioned type.
- the use of the emulsification technique with a non-solvent liquid makes it possible to envisage applying the method according to the invention not only to non-absorbent surfaces, but also to bodies such as unvarnished ceramics. , sintered, woven, etc.
- This process can therefore be implemented not only for example in the technical fields of electroplating, the manufacture of silicon wafers, printed circuits, etc., but also in photolithography, in the manufacture and development of photographic films, the treatment and in particular the dyeing of textiles, the leather industry, the chemical industry, that of mining, etc.
- the parts to be rinsed (not shown) are introduced directly into a tank or container 1 containing the cold LFI 2 (room temperature).
- Ultrasonic transducers 3 are activated to allow the emulsification of the liquid to be eliminated by the LFI.
- This emulsion is subjected to an upward movement, because its density is less than that of the LFI on the one hand, and on the other hand because the LFI is introduced into the tank 1 from the bottom, by means of a pump. recirculation 4 and via an intermediate filter 5.
- the emulsion 6 therefore overflows from the tank 1 and is directed towards a high-voltage demulsifier 7.
- This demulsifier 7 comprises an axial filiform electrode 8 connected to a high voltage source and a conductive cylindrical body connected to the ground.
- the emulsion is then broken by the union of the micro-droplets in large drops.
- the mixture LFI / large drops 9 of liquid to be eliminated then passes through a decanter 10 or Florentine vase.
- the aqueous liquid to be eliminated less dense than the LFI, floats on the surface of the latter and, by successive additions, overflows through the discharge pipe 11; this aqueous liquid is recovered and can be reused directly as such upstream of the manufacturing process.
- the LFI it passes under the baffle 10 'and overflows into the tank 12 of the decanter 10, this part of the tank serving as a container for balancing variations in levels of the entire installation.
- the pump 4 draws off the dry and clean LFI from the tank 12, which then passes through a filter 5 and enters the tank 1 through the bottom and through anti-turbulence flaps 13, thus pushing emulsion upward, like a plunger, to quickly replace the emulsion with dry, clean LFI.
- a turbidity detection device 14 determines the end of the emulsification process, that is to say as soon as the LFI is perfectly clear and without cloudiness, which means that the surfaces to be rinsed are then completely rid of the aqueous liquid to be eliminate.
- Another possibility of control consists in inserting a voltage detector and / or a current detector in the high-voltage supply circuit of the demulsifier, the voltage being inversely proportional and the current being proportional to the quantity of micro-droplets arriving in the demulsifier .
- the parts are then removed from the first rinsing zone in the liquid phase (tank 1) and they pass into a second rinsing zone 15 in the vapor phase containing the vapors of the LFI liquid.
- These vapors are produced by two boilers 16 heated by heating bodies 17 and supplied with LFI by the tank 12.
- a level detection system 18 controls the valves 19.
- the recondensed LFI flows along the walls and is brought into a decanter (Florentine vase) 22, together with a small amount of water from the humidity of the ambient air and also condensed on the walls of the double -coat, water which floats on the surface of the denser LFI and, by successive additions, overflows by a pipe 23 to be evacuated to the sewer.
- the LFI thus distilled, is reintroduced by gravity into the bottom of the tank 1.
- the impurities brought to the system are collected either in the filter 5, or at the bottom of the boilers 16.
- a check valve return 24 has been provided to prevent the LFI from tank 1 from emptying by gravity into tank 12.
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Abstract
Description
La présente invention se rapporte à un procédé de rinçage de surfaces sans utilisation d'eau, et à une installation pour la mise en oeuvre de ce procédé.The present invention relates to a process for rinsing surfaces without the use of water, and to an installation for implementing this process.
Pour le rinçage de surfaces ayant été soumises à un traitement physique, chimique ou électrochimique en milieu aqueux (dépôt galvanique d'un revêtement, gravure, polissage, trempe, dégraissage, décapage, développement et fixation, oxydation, coloration, etc.) ou de surfaces ayant été formées en milieu aqueux (par cristallisation, précipitation, etc.), pratiquement toutes les méthodes actuellement connues et largement utilisées industriellement impliquent comme première étape le rinçage des pièces à l'eau, puis l'élimination de celle-ci desdites surfaces.For rinsing surfaces that have been subjected to a physical, chemical or electrochemical treatment in an aqueous medium (galvanic deposition of a coating, etching, polishing, tempering, degreasing, pickling, development and fixing, oxidation, coloring, etc.) or surfaces having been formed in an aqueous medium (by crystallization, precipitation, etc.), practically all of the methods currently known and widely used industrially involve, as a first step, rinsing the parts with water, then eliminating the latter from said surfaces .
Ce type de méthode présente toutefois au moins deux inconvénients, à savoir qu'elle conduit à la formation de quantités importantes d'eau polluée qui sont incompatibles avec les exigences, actuellement de plus en plus sévères, de protection de l'environnement, et que les solutions aqueuses ainsi éliminées des surfaces, même si elles peuvent être récupérées, sont généralement dégradées et inutilisables.However, this type of method has at least two drawbacks, namely that it leads to the formation of large quantities of polluted water which are incompatible with the requirements, currently increasingly severe, of environmental protection, and that aqueous solutions thus removed from surfaces, even if they can be recovered, are generally degraded and unusable.
Quant au séchage subséquent, la plus ancienne méthode connue consiste en l'évaporation libre ou forcée de l'eau dans l'atmosphére, ce qui implique comme inconvénients majeurs la formation de taches et l'oxydation des surfaces, généralement inadmissibles. Des méthodes plus modernes sont basées sur l'utilisation de liquides hydrofuges pour éliminer l'eau des surfaces, ces liquides contenant des agents tensioactifs rendant les surfaces traitées hydrophobes, donc non mouillables par l'eau. D'autres méthodes utilisent des bains tels que du trichloréthylène ou perchlo- réthylène bouillants également additionnés d'agents tensioactifs. L'eau est ainsi éliminée par formation d'azéotropes, c'est-à-dire par solubilisation d'eau dans le solvant (7 % d'eau dans l'azéotrope trichloréthylène-eau); il n'y a dans ce cas que peu ou pas d'oxydation des surfaces, mais le problème des taches n'est pas résolu pour autant.As for subsequent drying, the oldest known method consists in the free or forced evaporation of water in the atmosphere, which implies as major drawbacks the formation of stains and oxidation of surfaces, generally inadmissible. More modern methods are based on the use of water-repellent liquids to remove water from surfaces, these liquids containing surfactants making the treated surfaces hydrophobic, therefore not wettable by water. Other methods use baths such as boiling trichlorethylene or perchloroethylene, also containing surfactants. The water is thus eliminated by the formation of azeotropes, that is to say by solubilization of water in the solvent (7% of water in the azeotrope trichlorethylene-water); in this case there is little or no oxidation of the surfaces, but the problem of stains is not resolved however.
Le dernier inconvénient précité a pu être partiellement éliminé par l'utilisation de solvants chlorofluorés, également utilisables directement comme agents de nettoyage, dégraissage, rinçage et/ou séchage, seuls ou en mélange avec d'autres produits tels que des alcools et des agents tensioactifs. Par exemple, le brevet US 3.397.150 décrit un moyen pour éliminer l'eau comprenant un mélange de trichlorotrifluoroé- thane et d'un agent tensioactif constitué par un produit de neutralisation d'éthers alkyliques d'acide phosphorique avec une amine aliphatique et formant avec l'eau un mélange azéotropique contenant environ 1 % d'eau. La demande de brevet FR-A-2 213 788 décrit un procédé pour éliminer l'eau d'une surface en rendant celle-ci hydrophobe, grâce à la mise en oeuvre d'un bain comprenant des solvants chlorés ou chlorofluorés non miscibles à l'eau, en mélange avec des solvants miscibles à l'eau tels que l'isopropa- nol, généralement additionné d'agents tensioactifs du type de ceux décrits dans le brevet US 3.397.150 et formant avec l'eau un mélange azéotropique.The last aforementioned drawback has been partially eliminated by the use of chlorofluorinated solvents, which can also be used directly as cleaning, degreasing, rinsing and / or drying agents, alone or as a mixture with other products such as alcohols and surfactants. . For example, US Patent 3,397,150 describes a means for removing water comprising a mixture of trichlorotrifluoroethane and a surfactant consisting of a product for neutralizing alkyl ethers of phosphoric acid with an aliphatic amine and forming with water an azeotropic mixture containing about 1% water. Patent application FR-A-2 213 788 describes a process for removing water from a surface by making it hydrophobic, by using a bath comprising chlorinated or chlorofluorinated solvents immiscible with water. water, mixed with water-miscible solvents such as isopropanol, generally containing surfactants of the type described in US Pat. No. 3,397,150 and forming an azeotropic mixture with water.
Quant au brevet US 4.169.807, il décrit comme moyen de séchage de pièces à base de silicum des mélanges contenant du propanol, de l'eau et certains composés perfluorés.As for US patent 4,169,807, it describes as a means of drying silicon-based parts mixtures containing propanol, water and certain perfluorinated compounds.
L'inconvénient majeur de ces méthodes mettant pratiquement toujours en oeuvre un agent tensioactif destiné à transformer les surfaces hydrophiles en surfaces hydrophobes, en plus des inconvénients déjà cités relatifs à l'utilisation d'eau de rinçage, consiste en ce que l'élimination complète de l'agent tensioactif est souvent difficile voire impossible à obtenir dans des conditions industrielles. Or, la présence à la surface d'une pièce d'un tel film hydrophobe, même monomoléculaire, d'agent tensioactif peut se révéler très néfaste par exemple dans le cas d'un traitement subséquent galvanique ou autre. D'autre part, lorsque le liquide à éliminer d'une surface est par exemple une solution galvanique, le fait qu'il y ait utilisation de bains de liquides solvants et formation de mélanges azéotropiques entre les deux phases liquides implique un phénomène d'extraction liquide-liquide et donc une altération du bain galvanique, lequel ne pourra plus être réutilisé tel quel.The major drawback of these methods practically always using a surfactant intended to transform hydrophilic surfaces into hydrophobic surfaces, in addition to the drawbacks already mentioned relating to the use of rinse water, consists in that the complete elimination surfactant is often difficult or even impossible to obtain under industrial conditions. However, the presence on the surface of a part of such a hydrophobic film, even a monomolecular film, of surfactant can prove to be very harmful, for example in the case of a subsequent galvanic or other treatment. On the other hand, when the liquid to be removed from a surface is for example a galvanic solution, the fact that there is use of baths of solvent liquids and formation of azeotropic mixtures between the two liquid phases implies an extraction phenomenon liquid-liquid and therefore an alteration of the galvanic bath, which can no longer be reused as it is.
En conséquence, le but de cette invention consiste à obvier aux inconvénients des méthodes connues pour le rinçage de surfaces, en fournissant un procédé qui ne nécessite pas l'utilisation d'eau, ni d'agents tensioactifs, ni de bains de solvants susceptibles de favoriser la formation de mélanges azéotropiques ou de conduire à des extractions liquides-liquides, et qui permette de maintenir les surfaces traitées hydrophiles et de récupérer le liquide aqueux éliminé sans l'altérer.Consequently, the aim of this invention is to obviate the drawbacks of the known methods for rinsing surfaces, by providing a process which does not require the use of water, nor of surfactants, nor of baths of solvents capable of favor the formation of azeotropic mixtures or lead to liquid-liquid extractions, and which makes it possible to maintain the treated surfaces hydrophilic and to recover the aqueous liquid eliminated without altering it.
Le procédé selon l'invention visant à atteindre le but ci-dessus, présente les caractéristiques mentionnées dans la revendication 1.The method according to the invention aimed at achieving the above object has the characteristics mentioned in claim 1.
De préférence, le liquide non solvant destiné à former une émulsion avec le liquide aqueux à éliminer est choisi parmi les composés organiques complètement fluorés. Dans la suite de la présente description, ces composés seront dénommés LFI (= Liquides Fluorés Inertes).Preferably, the non-solvent liquid intended to form an emulsion with the aqueous liquid to be eliminated is chosen from completely fluorinated organic compounds. In the remainder of this description, these compounds will be referred to as LFI (= Inert Fluorinated Liquids).
Un autre objet de cette invention consiste en une installation pour la mise en oeuvre du procédé selon l'invention, qui présente les caractéristiques définies dans la revendication 3.Another object of this invention consists of an installation for implementing the method according to the invention, which has the characteristics defined in
Le dessin annexé illustre schématiquement et à tire d'exemple une réalisation d'une installation selon l'invention pour le rinçage de surfaces.The appended drawing illustrates schematically and by way of example an embodiment of an installation according to the invention for rinsing surfaces.
Tant en ce qui concerne la formation de l'émulsion, que le cassage et la séparation de celle-ci après récupération, on peut utiliser n'importe quelle technique connue.As far as the formation of the emulsion is concerned, as well as the breaking and separation of the latter after recovery, any known technique can be used.
Pour ce qui est de la formation de l'émulsion, on peut utiliser un récipient contenant le LFI et dans lequel les pièces sont immergées. Celles-ci peuvent être déposées en vrac dans des paniers ou des tambours, montées sur des racks prévus à cet effet, ou bien suspendues dans le cas de pièces de plus grandes dimensions, ou bien maintenues dans le LFI par n'importe quel type de support, ou encore dans le cas d'une technique en continu sous la forme d'un passage en bande, en fil, en film, etc.As regards the formation of the emulsion, a container containing the LFI can be used and in which the parts are immersed. These can be placed in bulk in baskets or drums, mounted on racks provided for this purpose, or suspended in the case of larger pieces, or held in the LFI by any type of support, or also in the case of a continuous technique in the form of a passage in strip, wire, film, etc.
L'émulsion est obtenue de préférence par application d'ultrasons, par exemple à des fréquences généralement comprises entre 20 et 80 kHz, ou par agitation et vibration plus ou moins énergique des pièces à traiter immergées soit transmise mécaniquement par une source externe, soit induite électromagnétiquement à l'intérieur des pièces, ou encore par vibration du récipient lui- même et transmission aux pièces immergées par le liquide. Ces techniques et plus particulièrement celle mettant en oeuvre des ultrasons sont notamment appropriées pour le traitement de pièces relativement petites et coûteuses dans des installations de petites dimensions.The emulsion is preferably obtained by application of ultrasound, for example at frequencies generally between 20 and 80 kHz, or by more or less energetic agitation and vibration of the parts to be treated immersed either mechanically transmitted by an external source, or induced electromagnetically inside the parts, or by vibration of the container itself and transmission to the parts submerged by the liquid. These techniques and more particularly that using ultrasound are particularly suitable for the treatment of relatively small and costly parts in small installations.
Pour des pièces aux formes simples, telles que fils et bandes, on peut utiliser des techniques de giclage et d'aspersion à des pressions plus ou moins élevées.For parts with simple shapes, such as wires and strips, spraying and spraying techniques can be used at higher or lower pressures.
Enfin, pour des pièces lourdes et de relativement grandes dimensions, traitées dans des installations volumineuses, un procédé du type "Hydroson" décrit dans la publication "Ober- flàche-Surface" no 21, 12/1980) est applicable.Finally, for heavy and relatively large parts, treated in bulky installations, a "Hydroson" type process described in the publication "Oberflàche-Surface"
Comme déjà mentionné, le liquide non solvant inerte employé dans le procédé selon l'invention est de préférence un composé organique complètement fluoré, par exemple du type "Fluorinert" (de la société 3M). Ces composés, dérivés de composés organiques communs par remplacement de tous les atomes d'hydrogène, par des atomes de fluor, ne contiennent donc ni hydrogène, ni chlore. Ils sont non polaires et n'ont pratiquement aucune action de solvant, notamment à l'égard de l'eau et des constituants des liquides aqueux industriels tels que les bains galvaniques. Ils sont incolores, inodores, faiblement toxiques et ininflammables, mais surtout présentent une stabilité thermique élevée et sont chimiquement inertes. Ces composés LFI sont donc quant à leurs propriétés complètement différents des solvants chlorofluorés habituellement employés comme solvants, agents de dégraissage, et de séchage, etc. De plus, par rapport à ceux-ci, l'exceptionnelle inertie chimique des LFI fait qu'ils ne rendent pas les surfaces traitées hydrophobes, ne contaminent ou modifient en rien les solutions aqueuses qu'ils émulsionnent, celles-ci pouvant donc être réutilisées directement en amont du processus de fabrication, après démulsification.As already mentioned, the inert non-solvent liquid used in the process according to the invention is preferably a completely fluorinated organic compound, for example of the "Fluorinert" type (from the company 3M). These compounds, derived from common organic compounds by replacement of all the hydrogen atoms, by fluorine atoms, therefore contain neither hydrogen nor chlorine. They are non-polar and have practically no solvent action, in particular with regard to water and the constituents of industrial aqueous liquids such as galvanic baths. They are colorless, odorless, slightly toxic and non-flammable, but above all have high thermal stability and are chemically inert. These LFI compounds are therefore completely different in their properties from the chlorofluorinated solvents usually used as solvents, degreasing and drying agents, etc. In addition, compared to these, the exceptional chemical inertness of LFIs means that they do not make the treated surfaces hydrophobic, do not contaminate or modify in any way the aqueous solutions that they emulsify, these can therefore be reused directly upstream of the manufacturing process, after demulsification.
Certains agents tensioactifs fluorés stables peuvent se dissoudre dans une certaine mesure dans les LFI. Par conséquent, et bien que cela ne soit pas nécessaire en général, il peut être dans certains cas utile d'en incorporer au LFI, pour autant bien entendu qu'ils ne risquent pas de rendre les surfaces hydrophobes, et, afin d'augmenter l'efficacité et la rapidité du rinçage, surtout lorsque l'on met en oeuvre la technique du giclage/aspersion. Le même effet que ci-dessus peut aussi être obtenu en incorporant l'agent tensioactif fluoré stable au liquide aqueux à éliminer.Some stable fluorosurfactants can dissolve to some extent in LFIs. Consequently, and although this is not generally necessary, it may in certain cases be useful to incorporate it into the LFI, provided of course that they do not risk rendering the surfaces hydrophobic, and, in order to increase the effectiveness and speed of rinsing, especially when using the spraying / sprinkling technique. The same effect as above can also be obtained by incorporating the stable fluorosurfactant into the aqueous liquid to be removed.
L'emploi préféré de liquides organiques complètement fluorés n'exclut toutefois pas que d'autres produits partiellement fluorés, par exemple du type "Freon 113", puissent être également utilisés, dans certains cas et essentiellement pour des raisons économiques et/ou lorsque les exigences qualitatives des surfaces sont moins élevées. Dans ce cas, et pour compenser le pouvoir émulsionnant moindre, il est recommandé d'ajouter un agent tensioactif du type précité.The preferred use of completely fluorinated organic liquids does not however exclude that other partially fluorinated products, for example of the "Freon 113" type, can also be used, in certain cases and essentially for economic reasons and / or when the quality requirements of the surfaces are lower. In this case, and to compensate for the lower emulsifying power, it is recommended to add a surfactant of the aforementioned type.
En ce qui concerne les différentes possibilités de casser une émulsion, on peut citer notamment la centrifugation, l'action d'ultrasons à fréquence déterminée, la démulsification chimique, le passage de l'émulsion à travers une grille fine, un lit granulaire, un matériau poreux ou filamenteux, une membrane hydrophobe, etc., l'utilisation d'un effet thermique, de radiations ionisantes, d'un champ magnétique, la microflottation, l'ultrafiltration, etc. Il semble que la technique qui serait actuellement la mieux appropriée serait celle du séparateur ou démulsionneur à hautetension, du type de celui décrit par exemple dans le brevet US 1.533.711.As regards the different possibilities of breaking an emulsion, mention may be made in particular of centrifugation, the action of ultrasound at a fixed frequency, chemical demulsification, the passage of the emulsion through a fine grid, a granular bed, a porous or filamentary material, a hydrophobic membrane, etc., the use of a thermal effect, ionizing radiation, a magnetic field, microflotation, ultrafiltration, etc. It seems that the technique which would currently be the most suitable would be that of the high-voltage separator or demulsifier, of the type described for example in US Patent 1,533,711.
Enfin, en ce qui concerne le séchage des surfaces, on peut citer notamment le soufflage de gaz froid ou chaud, l'emploi de radiations infrarouges, l'évaporation libre, le chauffage par induction, le séchage en phase vapeur, etc. Il semble toutefois que la technique qui serait la mieux appropriée ici serait celle du séchage en phase vapeur, bien connue par les professionnels.Finally, with regard to the drying of surfaces, mention may be made in particular of the blowing of cold or hot gas, the use of infrared radiation, free evaporation, heating by induction, drying in the vapor phase, etc. However, it seems that the technique that would be most appropriate here would be that of vapor phase drying, well known by professionals.
La méthode préconisée par la présente invention offre donc, par rapport aux méthodes tra- dionnelles, les avantages très importants suivants:
- plus du tout ou beaucoup moins de pollution de l'environnement, et plus particulièrement des eaux;
- récupération intégrale et dans leur forme originale des liquides aqueux éliminés des surfaces, et donc également par exemple des métaux qu'ils contiennent;
- maintien des caractéristiques hydrophiles des surfaces traitées, celles-ci pouvant donc ensuite être soumises à des bains galvaniques ou autres sans perte de qualité;
- utilisation de beaucoup moins de place que par exemple celle nécessaire aux bacs de décantation;
- très importante diminution de la consommation d'eau, de la consommation des produits chimiques utilisés habituellement pour la neutralisation et la détoxication, de l'énergie thermique nécessaire par rapport à celle nécessaire à l'évaporation pour la concentration des eaux de rinçage; et
- possibilité d'utiliser des processus de fabrication éprouvés mais que de très importants problèmes de détoxication interdisent ou limitent l'emploi, comme par exemple l'utilisation de composés cyanurés, au cadmium, au chrome hexavalent 6, etc.
- no more or much less pollution of the environment, and more particularly of water;
- full recovery in their original form of aqueous liquids removed from surfaces, and therefore also, for example, of the metals they contain;
- maintenance of the hydrophilic characteristics of the treated surfaces, which can therefore then be subjected to galvanic or other baths without loss of quality;
- use of much less space than for example that necessary for the settling tanks;
- very significant reduction in water consumption, consumption of chemicals usually used for neutralization and detoxification, thermal energy required compared to that required for evaporation for the concentration of rinsing water; and
- possibility of using manufacturing processes proven but that very serious detoxification problems prohibit or limit the use, such as for example the use of cyanide compounds, cadmium,
hexavalent chromium 6, etc.
De plus, l'utilisation de la technique d'émul- sionnement avec un liquide non solvant permet d'envisager l'application du procédé selon l'invention non seulement aux surfaces non absorbantes, mais également à des corps tels que des céramiques non vernies, des frittés, des tissés, etc. Ce procédé peut donc être mis en oeuvre non seulement par exemple dans les domaines techniques de la galvanoplastie, de la fabrication des plaquettes de silicium, des circuits imprimés, etc., mais également en photolithographie, dans la fabrication et le développement de films photographiques, le traitement et notamment la teinture des textiles, l'industrie du cuir, l'industrie chimique, celle des mines, etc.In addition, the use of the emulsification technique with a non-solvent liquid makes it possible to envisage applying the method according to the invention not only to non-absorbent surfaces, but also to bodies such as unvarnished ceramics. , sintered, woven, etc. This process can therefore be implemented not only for example in the technical fields of electroplating, the manufacture of silicon wafers, printed circuits, etc., but also in photolithography, in the manufacture and development of photographic films, the treatment and in particular the dyeing of textiles, the leather industry, the chemical industry, that of mining, etc.
On décrira maintenant à titre d'exemple et en référence au dessin annexé une forme d'exécution du procédé et de l'installation selon l'invention.An embodiment of the method and of the installation according to the invention will now be described by way of example and with reference to the accompanying drawing.
Les pièces à rincer (non illustrées) sont introduites directement dans une cuve ou récipient 1 contenant le LFI 2 froid (température ambiante). Des transducteurs ultrasoniques 3 sont mis en action pour permettre l'émulsionnement du liquide à éliminer par le LFI. Cette émulsion est soumise à un mouvement ascendant, car sa densité est moindre que celle du LFI d'une part, et d'autre part du fait que le LFI est introduit dans la cuve 1 par le fond, au moyen d'une pompe de recirculation 4 et via un filtre intermédiaire 5. L'émulsion 6 déborde par conséquent de la cuve 1 et est dirigée vers un démulsionneur à haute tension 7.The parts to be rinsed (not shown) are introduced directly into a tank or container 1 containing the cold LFI 2 (room temperature).
Ce démulsionneur 7 comprend une électrode filiforme axiale 8 reliée à une source de hautetension et un corps cylindrique conducteur relié à la terre. L'émulsion est alors cassée par la réunion des micro-gouttelettes en grosses gouttes. Le mélange LFI/grosses gouttes 9 de liquide à éliminer passe ensuite dans un décanteur 10 ou vase florentin. Le liquide aqueux à éliminer, moins dense que le LFI, flotte à la surface de celui-ci et, par additions successives, déborde par le tuyau d'évacuation 11; ce liquide aqueux est récupéré et peut être réutilisé directement comme tel en amont du processus de fabrication. Quant au LFI, il passe sous la chicane 10' et déborde dans le réservoir 12 du décanteur 10, cette partie du réservoir faisant office de récipient d'équilibrage des variations de niveaux de toute l'installation.This demulsifier 7 comprises an axial
Comme on l'a déjà dit, la pompe 4 soutire le LFI, sec et propre du réservoir 12, qui passe alors par un filtre 5 et entre dans la cuve 1 par le fond et au travers de volets anti-turbulences 13, poussant ainsi l'émulsion vers le haut, comme un piston, afin de remplacer rapidement l'émulsion par du LFI sec et propre.As has already been said, the pump 4 draws off the dry and clean LFI from the
Un dispositif de détection de turbidité 14 détermine la fin du processus d'émulsionnement, c'est-à-dire dès que le LFI est parfaitement clair et sans trouble, ce qui signifie que les surfaces à rincer sont alors totalement débarrassées du liquide aqueux à éliminer. Une autre possibilité de contrôle consiste à insérer un détecteur de tension et/ou un détecteur de courant dans le circuit hautetension d'alimentation du démulsionneur, la tension étant inversément proportionnelle et le courant étant proportionnel à la quantité des micro-gouttelettes arrivant dans le démulsionneur.A turbidity detection device 14 determines the end of the emulsification process, that is to say as soon as the LFI is perfectly clear and without cloudiness, which means that the surfaces to be rinsed are then completely rid of the aqueous liquid to be eliminate. Another possibility of control consists in inserting a voltage detector and / or a current detector in the high-voltage supply circuit of the demulsifier, the voltage being inversely proportional and the current being proportional to the quantity of micro-droplets arriving in the demulsifier .
Les pièces sont ensuite retirées de la première zone de rinçage en phase liquide (cuve 1) et elles passent dans une seconde zone de rinçage 15 en phase vapeur contenant les vapeurs du liquide LFI. Ces vapeurs sont produites par deux bouilleurs 16 chauffés par des corps de chauffe 17 et alimentés en LFI par le réservoir 12. Un système de détection de niveau 18 asservit les vannes 19.The parts are then removed from the first rinsing zone in the liquid phase (tank 1) and they pass into a
Dans la zone des vapeurs 15, celles-ci se condensent sur les pièces qui sont extraites du LFI froid de la cuve 1, ce qui a pour conséquence que le liquide ainsi distillé, extrêmement pur, élimine par entraînement d'éventuelles impuretés pouvant se trouver encore sur les surfaces, et que l'énergie thermique des vapeurs est transférée aux pièces, qui s'échauffent donc. Une fois chaudes, les pièces peuvent alors être retirées de la zone des vapeurs 15 pour entrer dans la zone de séchage 20, dont les parois sont refroidies par un double-manteau 21, dans lequel circule un fluide réfrigérant (eau, "Fréon", etc.). Le refroidissement des parois peut être également assuré par un serpentin dans lequel circule un fluide réfrigérant. Ainsi, le LFI présent sur les pièces réchauffées par ce dernier s'évapore et se recondense sur les parois froides du double-manteau. Le LFI ainsi recondensé coule le long des parois et est amené dans un décanteur (vase florentin) 22, en même temps qu'une faible quantité d'eau provenant de l'humidité de l'air ambiant et également condensée sur les parois du double-manteau, eau qui surnage à la surface du LFI plus dense et, par additions successives, déborde par un tuyau 23 pour être évacuée à l'égout. Le LFI, ainsi distillé est réintroduit par gravité dans le bas de la cuve 1. Les impuretés amenées au système sont rassemblées soit dans le filtre 5, soit au fond des bouilleurs 16. Enfin, lorsque la pompe 4 ne tourne pas, un clapet anti-retour 24 a été prévu pour empêcher que le LFI de la cuve 1 ne vienne se vider par gravité dans le réservoir 12.In the
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86905186T ATE58187T1 (en) | 1985-09-13 | 1986-09-11 | METHOD AND DEVICE FOR FLUSHING SURFACES WITH NON-AQUEOUS LIQUIDS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH3984/85A CH663554A5 (en) | 1985-09-13 | 1985-09-13 | METHOD FOR RINSING SURFACES WITHOUT USING WATER, AND INSTALLATION FOR CARRYING OUT SAID METHOD. |
CH3984/85 | 1985-09-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0238517A1 EP0238517A1 (en) | 1987-09-30 |
EP0238517B1 true EP0238517B1 (en) | 1990-11-07 |
Family
ID=4267629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86905186A Expired - Lifetime EP0238517B1 (en) | 1985-09-13 | 1986-09-11 | Method and apparatus for rinsing surfaces with non-aqueous liquids |
Country Status (6)
Country | Link |
---|---|
US (2) | US4936921A (en) |
EP (1) | EP0238517B1 (en) |
JP (1) | JPS63501348A (en) |
CH (1) | CH663554A5 (en) |
DE (1) | DE3675540D1 (en) |
WO (1) | WO1987001740A1 (en) |
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US5183067A (en) * | 1988-07-08 | 1993-02-02 | Isc Chemicals Limited | Cleaning and drying of electronic assemblies |
JPH04260482A (en) * | 1991-02-15 | 1992-09-16 | Japan Field Kk | Method and apparatus for drying article to be washed after washing |
JPH04290586A (en) * | 1991-03-15 | 1992-10-15 | Japan Field Kk | Method and device for rinsing wash |
US5125978A (en) * | 1991-04-19 | 1992-06-30 | Minnesota Mining And Manufacturing Company | Water displacement composition and a method of use |
US5089152A (en) * | 1991-04-19 | 1992-02-18 | Minnesota Mining And Manufacturing Company | Water displacement composition |
JPH06258810A (en) * | 1993-03-08 | 1994-09-16 | Noritsu Koki Co Ltd | Photosensitive material carrying guide for automatic photographic processing machine |
US5466375A (en) * | 1993-07-21 | 1995-11-14 | Galik; George M. | Liquid-liquid extraction |
DE4415548A1 (en) * | 1994-05-03 | 1995-11-09 | Frembgen Fritz Herbert | Method for treating electrochemically machined workpieces |
US6045588A (en) * | 1997-04-29 | 2000-04-04 | Whirlpool Corporation | Non-aqueous washing apparatus and method |
US7534304B2 (en) * | 1997-04-29 | 2009-05-19 | Whirlpool Corporation | Non-aqueous washing machine and methods |
US7513132B2 (en) | 2003-10-31 | 2009-04-07 | Whirlpool Corporation | Non-aqueous washing machine with modular construction |
US6689925B2 (en) | 2001-05-11 | 2004-02-10 | Invifuel Ltd. | Conversion of drilling waste to fuel |
US6631682B2 (en) * | 2001-06-13 | 2003-10-14 | Telluckram Maharaj | Non-aqueous cleaning system and method for a printing press recirculation system |
US6417118B1 (en) * | 2001-06-26 | 2002-07-09 | United Microelectronics Corp. | Method for improving the moisture absorption of porous low dielectric film |
EP1446469A1 (en) * | 2001-11-20 | 2004-08-18 | Unilever N.V. | Process for cleaning a substrate |
US20040238119A1 (en) * | 2003-05-26 | 2004-12-02 | Ching-Yu Chang | [apparatus and method for etching silicon nitride thin film ] |
US20050096242A1 (en) * | 2003-10-31 | 2005-05-05 | Luckman Joel A. | Method for laundering fabric with a non-aqueous working fluid using a select rinse fluid |
US20050222002A1 (en) * | 2003-10-31 | 2005-10-06 | Luckman Joel A | Method for a semi-aqueous wash process |
US20050096243A1 (en) * | 2003-10-31 | 2005-05-05 | Luckman Joel A. | Fabric laundering using a select rinse fluid and wash fluids |
US20050091755A1 (en) * | 2003-10-31 | 2005-05-05 | Conrad Daniel C. | Non-aqueous washing machine & methods |
US7695524B2 (en) * | 2003-10-31 | 2010-04-13 | Whirlpool Corporation | Non-aqueous washing machine and methods |
US7739891B2 (en) * | 2003-10-31 | 2010-06-22 | Whirlpool Corporation | Fabric laundering apparatus adapted for using a select rinse fluid |
US7300468B2 (en) | 2003-10-31 | 2007-11-27 | Whirlpool Patents Company | Multifunctioning method utilizing a two phase non-aqueous extraction process |
US7513004B2 (en) * | 2003-10-31 | 2009-04-07 | Whirlpool Corporation | Method for fluid recovery in a semi-aqueous wash process |
US20050150059A1 (en) * | 2003-10-31 | 2005-07-14 | Luckman Joel A. | Non-aqueous washing apparatus and method |
US20050224099A1 (en) * | 2004-04-13 | 2005-10-13 | Luckman Joel A | Method and apparatus for cleaning objects in an automatic cleaning appliance using an oxidizing agent |
WO2005106105A1 (en) | 2004-04-29 | 2005-11-10 | Unilever N.V. | Dry cleaning method |
US7966684B2 (en) | 2005-05-23 | 2011-06-28 | Whirlpool Corporation | Methods and apparatus to accelerate the drying of aqueous working fluids |
CN105396826A (en) * | 2015-11-20 | 2016-03-16 | 无锡南方声学工程有限公司 | Rotary supporting frame structure of ultrasonic cleaning machine |
CN111233234B (en) * | 2020-01-16 | 2022-03-22 | 广东丽臣奥威实业有限公司 | Recovery process of surfactant in wastewater |
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US1533711A (en) * | 1924-11-20 | 1925-04-14 | Petroleum Hydrogenation Compan | Apparatus for and process of treating with high-tension currents |
GB718318A (en) * | 1952-06-24 | 1954-11-10 | Minnesota Mining & Mfg | Improvements in or relating to process of preparing cyclic fluoroalkylene oxide compounds and the cyclic fluoroalkylene oxide compounds resulting from said process |
US3397150A (en) * | 1966-03-15 | 1968-08-13 | Du Pont | Composition and method for treating surfaces |
US3386181A (en) * | 1966-11-15 | 1968-06-04 | Du Pont | Method of removing water and apparatus therefor |
US3710450A (en) * | 1971-02-01 | 1973-01-16 | Allied Chem | Process and apparatus for removing liquids from solid surfaces |
FR2213788A1 (en) * | 1973-01-16 | 1974-08-09 | Allied Chem | Drying appts - to remove liquid esp water from non-absorbent esp flat articles |
US3903012A (en) * | 1973-02-14 | 1975-09-02 | Du Pont | Water-displacement compositions containing fluorine compound and surfactant |
US4046154A (en) * | 1973-03-12 | 1977-09-06 | Fuji Photo Film Co., Ltd. | Apparatus for continuously removing film coating materials from film |
US3935076A (en) * | 1973-05-29 | 1976-01-27 | Canada-Cities Service, Ltd. | Two stage separation system |
US3957672A (en) * | 1973-11-23 | 1976-05-18 | The United States Of America As Represented By The Secretary Of The Navy | Displacement of organic liquid films from solid surfaces by non aqueous systems |
US3875046A (en) * | 1974-04-09 | 1975-04-01 | William J Rosenbloom | Recovery of oil from tar sand by an improved extraction process |
US4035282A (en) * | 1975-08-20 | 1977-07-12 | Shell Canada Limited | Process for recovery of bitumen from a bituminous froth |
DE2636993A1 (en) * | 1976-08-13 | 1978-02-23 | Schering Ag | METHOD FOR CLEANING OBJECTS AFTER GALVANIC AND / OR CHEMICAL SURFACE TREATMENT |
US4169807A (en) * | 1978-03-20 | 1979-10-02 | Rca Corporation | Novel solvent drying agent |
GB2104104A (en) * | 1981-08-14 | 1983-03-02 | Protective Finishing Group Lim | Cleaning of chemically treated articles |
FR2522007A1 (en) * | 1982-02-23 | 1983-08-26 | Ugine Kuhlmann | COMPOSITION FOR SURFACE WELDING |
-
1985
- 1985-09-13 CH CH3984/85A patent/CH663554A5/en not_active IP Right Cessation
-
1986
- 1986-09-11 JP JP61504668A patent/JPS63501348A/en active Pending
- 1986-09-11 WO PCT/CH1986/000130 patent/WO1987001740A1/en active IP Right Grant
- 1986-09-11 DE DE8686905186T patent/DE3675540D1/en not_active Expired - Lifetime
- 1986-09-11 EP EP86905186A patent/EP0238517B1/en not_active Expired - Lifetime
-
1988
- 1988-07-22 US US07/223,679 patent/US4936921A/en not_active Expired - Fee Related
-
1990
- 1990-02-02 US US07/473,873 patent/US5004000A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CH663554A5 (en) | 1987-12-31 |
EP0238517A1 (en) | 1987-09-30 |
DE3675540D1 (en) | 1990-12-13 |
US5004000A (en) | 1991-04-02 |
US4936921A (en) | 1990-06-26 |
WO1987001740A1 (en) | 1987-03-26 |
JPS63501348A (en) | 1988-05-26 |
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