EP0234425B1 - Process for cleaning aluminium containers - Google Patents

Process for cleaning aluminium containers Download PDF

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Publication number
EP0234425B1
EP0234425B1 EP87101975A EP87101975A EP0234425B1 EP 0234425 B1 EP0234425 B1 EP 0234425B1 EP 87101975 A EP87101975 A EP 87101975A EP 87101975 A EP87101975 A EP 87101975A EP 0234425 B1 EP0234425 B1 EP 0234425B1
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EP
European Patent Office
Prior art keywords
cleaning
solution
rinsing
process according
aluminum
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EP87101975A
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German (de)
French (fr)
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EP0234425A2 (en
EP0234425A3 (en
Inventor
Peter F. King
Karl A. Korinek
Thomas H. Fick
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Henkel Corp
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Henkel Corp
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Priority to AT87101975T priority Critical patent/ATE78066T1/en
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Classifications

    • 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
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • 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
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • the invention relates to a method for cleaning aluminum containers with the aid of alkaline cleaning solutions, the alkaline cleaning being preceded by a preliminary cleaning with an acidic solution and a rinsing with an aqueous solution, and its use as a pretreatment of aluminum containers before the application of conversion coatings.
  • Aluminum containers have found widespread use and are used in particular for packaging food and beverages, such as soft drinks and beer. It is common practice in the manufacture of such containers to first punch round disks from aluminum sheet, to bring them into a preliminary cup shape with suitable devices and finally to deform them in one or more stages by pulling and smoothing them into the final can. The cans are then trimmed and subjected to various cleaning and treatment stages. The conclusion is usually the application of an inner varnish and a decorative outer cover.
  • various lubricants and cooling lubricants are used which - together with fine metal particles that are formed during the shaping process - remain in certain quantities. It is essential that such lubricant residues and metal particles are removed before the containers are subjected to further treatment.
  • the type and thoroughness of the rinsing after the cleaning treatment is also of crucial importance for a possible taste impairment, but also the appearance of the surface.
  • the detergent solution adhering to the aluminum container and added to the rinsing stage must be practically completely removed.
  • the state of the art includes a process for cleaning aluminum containers with the help of alkaline cleaning solutions and subsequent water rinsing, in which one works in the rinsing stage with circulating rinsing water, which is kept approximately neutral to acidic by pH control (EP - A2 - 181 673).
  • this method has considerable advantages, particularly with regard to the consumption of rinsing water, the desired advantages with regard to the cleanliness of the containers and their mobility in the transport device of the treatment system and on the way from there to the further production stages, such as printing etc., cannot be achieved on a regular basis.
  • Another state-of-the-art method for cleaning aluminum containers by means of alkaline cleaning solutions provides for rinsing treatment with an aqueous solution, the pH of which is set to 2.5, to be followed (EP application 87 100 373.7).
  • an aqueous solution the pH of which is set to 2.5
  • One embodiment of the aforementioned method consists in rinsing with an acidic aqueous solution before the treatment with the alkaline cleaning solution. As a result, a considerable part of the impurities present on the aluminum container and consisting of fine aluminum particles and organic residues can be removed, so that the subsequent step of alkaline cleaning is less stressed.
  • US-A-4 540 444 relates to a process for the alkaline cleaning of aluminum containers with the following process steps: After performing an acid prewash, an acid cleaning is carried out. Following the acidic cleaning, a rinsing step is carried out, followed by the alkaline cleaning. This is followed by a rinse step with tap water, which is circulated, followed by a further rinse with fresh tap water. A rinse with deionized water is then carried out.
  • the object of the invention is to reduce this effort and still maintain the excellent results with regard to the regular maintenance of aluminum containers of high purity and with great mobility.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that at least part of the rinsing solution is introduced into the pre-cleaning stage.
  • the rinse solution used can be entered in the pre-cleaning stage without any special measures or after adding acid, especially sulfuric acid.
  • a solution is used in the pre-cleaning stage, the pH of which is adjusted to 4 to less than 7, preferably to 4.5 to 5.5.
  • the pre-cleaning with acidic solution has the advantage that the progressive increase in the concentration of emulsified oil and organic contaminants, which is accompanied by sludge formation, contamination of container walls and pipes and also leads to renewed settling on the aluminum containers, is avoided. Instead, oil and organic contaminants split off due to the breaking of the emulsion in the acidic medium, float and can be removed in the simplest way by stripping or decanting and the like.
  • a solution is used in the pre-cleaning stage which contains a surfactant.
  • surfactants can be anionic, cationic or nonionic in nature.
  • the pre-cleaning stage solution can be used at a temperature ranging from 15.5 ° C to 93.3 ° C. According to a particularly expedient embodiment of the invention, its temperature is set to ⁇ 65.6 ° C., in particular to a value from 32.2 to 54.4 ° C.
  • the solution can be applied in the usual way, e.g. by flooding, dipping or spraying. Spray treatment is preferred because of the uniform distribution of the solution over the inner and outer surfaces of the aluminum container.
  • Part of the solution from the pre-cleaning stage is withdrawn continuously or at certain intervals and sent to the wastewater treatment. This part is usually replaced quantitatively by acidified rinsing water.
  • alkaline cleaning takes place. It is preferably carried out using a cleaning solution which, in addition to alkaline components, contains a complexing agent and at least one surfactant with an HLB number of at least 12 and a pH of at least 10.
  • the alkaline component can be alkali or alkaline earth borate, carbonate, hydroxide or phosphate and mixtures thereof.
  • Alkali hydroxide and carbonate are the preferred ingredients.
  • concentration must be sufficient to remove the aluminum particles on the container surface, but on the other hand it must not cause excessive etching of the aluminum surface. The result must be a clean, shiny appearance of the surface.
  • the pH value which is capped at 10, can go up to around 13 depending on the nature of the container surface. It is preferably in the range from 11.5 to 12.5.
  • the concentration is usually between 0.05 and 10 g / l, preferably between 0.4 and 3.5 g / l.
  • the complexing agent must be soluble in the cleaning solution and compatible with the other components. He must also be able to complexly bind the ions in the solution to the extent that the formation of troublesome precipitates is avoided.
  • Sugar acids such as gluconic acid or glucoheptanoic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid or salts of these acids and sodium tripolyphosphate are particularly suitable as complexing agents.
  • the concentration of the complexing agents is usually in the range from 0.01 to 3 g / l, preferably in the range from 0.05 to 1 g / l.
  • the HLB number of the surfactant is a measure of the size and strength of the hydrophilic surfactant component in relation to the lipophilic surfactant component (cf. Römpps Chemie-Lexikon, Franckh'sche Verlagsbuch Kunststoff, Stuttgart, 8th edition, page 1715).
  • Suitable surfactants are, for example, those whose hydrophobic group is formed by alkylphenol, straight-chain or branched-chain alcohols and propylene glycol / propylene oxide polymers.
  • the hydrophilic constituent can originate from ethylene oxide groups, the end groups of which may be etherified or otherwise occupied.
  • Surfactants based on alkoxylated hydrocarbons are particularly suitable.
  • the aforementioned surfactants can be used individually or in combination. Their concentration should usually be 0.003 to 5 g / l, preferably 0.02 to 1.0 g / l.
  • the application of the cleaning solution is carried out as usual by e.g. Flooding, dipping or spraying at temperatures of about 15 to 65 ° C, preferably 32 to 54 ° C, for a period of time that ensures the purity of the aluminum surface.
  • a rinsing treatment with an aqueous solution is carried out, preferably in several stages.
  • the pH of the rinsing solution should be below 7.5, preferably 6.5 to 7. At higher pH values, the aluminum containers can easily turn brown when the treatment system is at a standstill in the area of the rinsing zone.
  • the final rinse is generally carried out with deionized water.
  • the aluminum containers are dried after the rinsing treatment, usually also painted, printed or otherwise provided with decorative coatings.
  • the method according to the invention is particularly advantageously suitable for the treatment of aluminum containers before the formation of conversion coatings.
  • Conversion coatings greatly improve the mobility of the containers (rotation, sliding against each other) as they pass through the treatment plant and through the subsequent production stages and also increase the corrosion resistance.
  • Such conversion coatings can be produced, for example, from solutions based on heavy metal phosphate or titanium, zirconium and hafnium fluoride with or without additional tannin content. Examples of methods for forming such conversion coatings are given in U.S. Patents 4,017,334, 4,054,466 and 4,338,140.
  • the aforementioned drying, painting, etc. usually follows, depending on the type of process, after a previous rinsing treatment.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Processing Of Solid Wastes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Aluminium containers are cleaned using alkaline cleaning solns., in which the alkaline cleaning is preceded by a precleaning with an aq. acidic soln. and followed by rinsing with an aq. soln. wherein at least a part of the rinsing soln. is employed in the precleaning step. A soln. of pH from 4 to less than 7, pref. 4.5-5.5 is employed in the precleaning step. The soln. contains 0.005-5 g/l, pref. 0.1-1 g/l, of a tensile, and has a temp. of less than 65.6 deg.C, esp. 32.2-54.4 deg.C.

Description

Die Erfindung betrifft ein Verfahren zur Reinigung von Aluminiumbehältern mit Hilfe von alkalischen Reinigerlösungen, wobei der alkalischen Reinigung eine Vorreinigung mit einer sauren Lösung vorgeschaltet und eine Spülung mit wäßriger Lösung nachgeschaltet ist, sowie dessen Anwendung als Vorbehandlung von Aluminiumbehältern vor dem Aufbringen von Konversionsüberzügen.The invention relates to a method for cleaning aluminum containers with the aid of alkaline cleaning solutions, the alkaline cleaning being preceded by a preliminary cleaning with an acidic solution and a rinsing with an aqueous solution, and its use as a pretreatment of aluminum containers before the application of conversion coatings.

Aluminiumbehälter haben weite Verbreitung gefunden und finden insbesondere zur Verpackung von Nahrungsmitteln und Getränken, wie alkoholfreie Getränke und Bier, Verwendung. Gängige Praxis bei der Herstellung derartiger Behälter ist es, zunächst aus Aluminiumblech runde Scheiben zu stanzen, diese mit geeigneten Vorrichtungen in eine vorläufige Napfform zu bringen und schließlich in einer oder mehreren Stufen durch Ziehen und Glätten zur endgültigen Dose zu verformen. Danach werden die Dosen besäumt und verschiedenen Reinigungs- und Behandlungsstufen unterworfen. Den Abschluß bildet üblicherweise die Aufbringung eines Innenlackes und eines dekorativen Au- ßenüberzugs.Aluminum containers have found widespread use and are used in particular for packaging food and beverages, such as soft drinks and beer. It is common practice in the manufacture of such containers to first punch round disks from aluminum sheet, to bring them into a preliminary cup shape with suitable devices and finally to deform them in one or more stages by pulling and smoothing them into the final can. The cans are then trimmed and subjected to various cleaning and treatment stages. The conclusion is usually the application of an inner varnish and a decorative outer cover.

Zur Erleichterung des vorgenannten Verfahrensganges mit Walzen, Stanzen, Ziehen und Glätten werden verschiedene Schmiermittel und Kühlschmierstoffe eingesetzt, die - zusammen mit feinen Metallteilchen, die während des Verformungsvorganges gebildet werden - in gewissen Mengen zurückbleiben. Es ist wesentlich, daß derartige Schmiermittelreste und Metallteilchen entfernt werden, bevor die Behälter einer weiteren Behandlung unterworfen werden.To facilitate the aforementioned process with rolling, punching, drawing and smoothing, various lubricants and cooling lubricants are used which - together with fine metal particles that are formed during the shaping process - remain in certain quantities. It is essential that such lubricant residues and metal particles are removed before the containers are subjected to further treatment.

Zu diesem Zweck gibt es zahlreiche saure oder alkalische Reiniger. Obgleich diese Reiniger im Hinblick auf die Rückstandsentfernung durchaus wirksam sind, ergeben sich häufig Probleme bezüglich einer Geschmacksbeeinträchtigung des Behälterinhalts. Dieses Problem ist insbesondere deswegen ärgerlich, weil es nur gelegentlich und in unvorhersehbarer Weise auftritt und dann zur Zurückweisung ganzer Dosen-Chargen wegen Beeinträchtigung des Doseninhalts führt. Die eigentlichen Gründe für das plötzliche Auftreten derartiger Geschmacksbeeinträchtigungen sind nicht bekannt. Eine etwas spekulative Vermutung geht dahin, daß von der Reinigung und einer eventuellen chemischen Behandlung verbleibende Rückstände zu dem fraglichen Problem führen. Anpassungen bzw. Veränderungen der Konzentration der wirksamen Bestandteile der Reinigerlösung sind insoweit ohne Wirkung. Außerdem sind der Größe der Veränderung der Konzentrationen der wirksamen Bestandteile Grenzen gesetzt, da sie zu nachteiligen Auswirkungen bezüglich der Aluminiumoberflächen führen, z.B. einem unerwünschten matten Aussehen.There are numerous acidic or alkaline cleaners for this purpose. Although these cleaners are quite effective in terms of residue removal, problems often arise with regard to the taste of the contents of the container. This problem is particularly annoying because it occurs only occasionally and in an unpredictable manner and then leads to rejection of entire batches of cans due to impairment of the contents of the can. The actual reasons for the sudden appearance of such taste impairments are not known. A somewhat speculative assumption is that residues from cleaning and any chemical treatment lead to the problem in question. In this respect, adjustments or changes in the concentration of the active components of the cleaning solution have no effect. In addition, there is a limit to the amount of change in the concentrations of the active ingredients since they lead to adverse effects on the aluminum surfaces, e.g. an undesirable matt appearance.

Von wesentlicher Bedeutung für eine eventuelle Geschmacksbeeinträchtigung, aber auch das Aussehen der Oberfläche, ist zudem die Art und Gründlichkeit der Spülung nach der Reinigungsbehandlung. Dabei muß insbesondere die dem Aluminiumbehälter anhaftende und in die Spülstufe eingetragene Reinigerlösung praktisch vollständig entfernt werden.The type and thoroughness of the rinsing after the cleaning treatment is also of crucial importance for a possible taste impairment, but also the appearance of the surface. In particular, the detergent solution adhering to the aluminum container and added to the rinsing stage must be practically completely removed.

Zum Stand der Technik gehört ein Verfahren zur Reinigung von Aluminiumbehältern mit Hilfe von alkalischen Reinigerlösungen und anschließende Wasserspülung, bei dem man in der Spülstufe mit im Kreislauf geführtem Spülwasser, das durch pH-Wert-Kontrolle etwa neutral bis sauer gehalten wird, arbeitet (EP - A2 - 181 673). Obgleich dieses Verfahren insbesondere auch im Hinblick auf den Spülwasserverbrauch beträchtliche Vorteile besitzt, sind nicht regelmäßig die erwünschten Vorteile hinsichtlich Reinheit der Behälter und deren Beweglichkeit in der Transporteinrichtung der Behandlungsanlage sowie auf dem Weg von dort zu den weiteren Fertigungsstufen, wie Bedrucken etc., erzielbar.The state of the art includes a process for cleaning aluminum containers with the help of alkaline cleaning solutions and subsequent water rinsing, in which one works in the rinsing stage with circulating rinsing water, which is kept approximately neutral to acidic by pH control (EP - A2 - 181 673). Although this method has considerable advantages, particularly with regard to the consumption of rinsing water, the desired advantages with regard to the cleanliness of the containers and their mobility in the transport device of the treatment system and on the way from there to the further production stages, such as printing etc., cannot be achieved on a regular basis.

Ein weiteres zum Stand der Technik gehöriges Verfahren zur Reinigung von Aluminiumbehältern mittels alkalischer Reinigerlösungen sieht vor, eine Spülbehandlung mit einer wäßrigen Lösung, deren pH-Wert auf 2,5 eingestellt ist, nachzuschalten (EP-Anmeldung 87 100 373.7). Mit Hilfe dieses Verfahrens gelingt es, mit großer Regelmäßigkeit zu Aluminiumbehältern zu gelangen, die sich durch hohe Reinheit auszeichnen und infolge der dadurch erzielten Beweglichkeit hohe Durchsatzleistungen, insbesondere auch in einer ggf. nachgeschalteten Bedruckungsvorrichtung, gestatten. Eine Ausgestaltung des vorgenannten Verfahrens besteht darin, vor der Behandlung mit der alkalischen Reinigerlösung mit einer sauren wäßrigen Lösung zu spülen. Hierdurch läßt sich bereits ein erheblicher Teil der auf dem Aluminiumbehälter befindlichen, aus feinen Aluminiumteilchen und organischen Rückständen bestehenden Verunreinigungen entfernen, so daß die nachfolgende Stufe der alkalischen Reinigung weniger stark belastet wird.Another state-of-the-art method for cleaning aluminum containers by means of alkaline cleaning solutions provides for rinsing treatment with an aqueous solution, the pH of which is set to 2.5, to be followed (EP application 87 100 373.7). With the aid of this method, it is possible to obtain aluminum containers with great regularity, which are distinguished by high purity and, as a result of the mobility thereby achieved, permit high throughput rates, in particular also in a printing device which may be connected downstream. One embodiment of the aforementioned method consists in rinsing with an acidic aqueous solution before the treatment with the alkaline cleaning solution. As a result, a considerable part of the impurities present on the aluminum container and consisting of fine aluminum particles and organic residues can be removed, so that the subsequent step of alkaline cleaning is less stressed.

Obgleich dieses Verfahren mit der genannten speziellen Ausgestaltung mit hervorragenden Ergebnissen verbunden ist, erfordert es doch einigen Aufwand an Vor- und Nachspülmitteln.Although this method is associated with the above-mentioned special design with excellent results, it does require some effort in pre-rinsing and rinsing agents.

US-A-4 540 444 betrifft ein Verfahren zur alkalischen Reinigung von Aluminiumbehältern mit folgenden Verfahrensschritten: Nach Durchführung einer sauren Vorwäsche wird eine saure Reinigung durchgeführt. Im Anschluß an die saure Reinigung wird ein Spülschritt durchgeführt, dem die alkalische Reinigung folgt. Daran anschließend folgt ein Spülschritt mit Leitungswasser, das im Kreis geführt wird, gefolgt von einer weiteren Spülung mit frischen Leitungswasser. Im Anschluß daran wird eine Spülung mit entionisiertem Wasser durchgeführt.US-A-4 540 444 relates to a process for the alkaline cleaning of aluminum containers with the following process steps: After performing an acid prewash, an acid cleaning is carried out. Following the acidic cleaning, a rinsing step is carried out, followed by the alkaline cleaning. This is followed by a rinse step with tap water, which is circulated, followed by a further rinse with fresh tap water. A rinse with deionized water is then carried out.

Aufgabe der Erfindung ist, diesen Aufwand zu Verringern und dennoch die hervorragenden Ergebnisse hinsichtlich des regelmäßigen Erhalts von Aluminiumbehältern hoher Reinheit und mit großer Beweglichkeit beizubehalten.The object of the invention is to reduce this effort and still maintain the excellent results with regard to the regular maintenance of aluminum containers of high purity and with great mobility.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man mindestens einen Teil der Spüllösung in die Stufe der Vorreinigung einträgt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that at least part of the rinsing solution is introduced into the pre-cleaning stage.

Je nach pH-Wert Einstellung kann benutzte Nachspüllösung ohne besondere Maßnahmen oder aber nach Zugabe von Säure, insbesondere von Schwefelsäure, in die Stufe der Vorreinigung eingetragen werden.Depending on the pH setting, the rinse solution used can be entered in the pre-cleaning stage without any special measures or after adding acid, especially sulfuric acid.

Erfindungsgemäß setzt man in der Vorreinigungsstufe eine Lösung ein, deren pH-Wert auf 4 bis kleiner als 7, vorzugsweise auf 4,5 bis 5,5, eingestellt ist.According to the invention, a solution is used in the pre-cleaning stage, the pH of which is adjusted to 4 to less than 7, preferably to 4.5 to 5.5.

Im Unterschied zu der im allgemeinen üblichen kaskadenartigen Führung der Reinigerlösung in der Reinigungsstufe, d.h. mit alkalischer Vorreinigung, hat die Vorreinigung mit saurer Lösung den Vorzug, daß fortschreitendes Anwachsen der Konzentration von emulgiertem Öl und organischen Verunreinigungen, das von Schlammbildung, Verschmutzung von Behälterwandungen und Rohrleitungen begleitet ist und zudem auch zu erneutem Absetzen auf den Aluminiumbehältern führt, vermieden wird. Statt dessen spalten sich Öl und organische Verunreinigungen infolge des Brechens der Emulsion im sauren Medium ab, schwimmen auf und können in einfachster Weise durch Abstreifen oder Dekantieren und dergl. abgetrennt werden.In contrast to the generally common cascade-like guidance of the cleaning solution in the cleaning stage, i.e. with alkaline pre-cleaning, the pre-cleaning with acidic solution has the advantage that the progressive increase in the concentration of emulsified oil and organic contaminants, which is accompanied by sludge formation, contamination of container walls and pipes and also leads to renewed settling on the aluminum containers, is avoided. Instead, oil and organic contaminants split off due to the breaking of the emulsion in the acidic medium, float and can be removed in the simplest way by stripping or decanting and the like.

Der vorgenannte Effekt kann verstärkt werden, wenn man gemäß einer weiteren vorteilhaften Ausgestaltung der Erfindung in der Vorreinigungsstufe eine Lösung einsetzt, die ein Tensid enthält. Hierbei sind Konzentrationen von 0,005 bis 5 g/I, vorzugsweise von 0,1 bis 1 g/I, besonders zweckmäßig. The aforementioned effect can be enhanced if, according to a further advantageous embodiment of the invention, a solution is used in the pre-cleaning stage which contains a surfactant. Concentrations of 0.005 to 5 g / l, preferably 0.1 to 1 g / l, are particularly expedient .

Diese Tenside können anionischer, kationischer oder nichtionischer Art sein.These surfactants can be anionic, cationic or nonionic in nature.

Die Lösung der Vorreinigungsstufe kann bei einer Temperatur, die von 15,5°C bis 93,3 °C reicht, eingesetzt werden. Entsprechend einer besonders zweckmäßigen Ausführungsform der Erfindung wird deren Temperatur auf < 65,6 °C, insbesondere auf einen Wert von 32,2 bis 54,4 °C, eingestellt. Die Applikation der Lösung kann auf übliche Weise, z.B. durch Fluten, Tauchen oder Spritzen, erfolgen. Die Spritzbehandlung ist wegen der gleichmäßigen Verteilung der Lösung auf die innere und äußere Oberfläche des Aluminiumbehälters bevorzugt.The pre-cleaning stage solution can be used at a temperature ranging from 15.5 ° C to 93.3 ° C. According to a particularly expedient embodiment of the invention, its temperature is set to <65.6 ° C., in particular to a value from 32.2 to 54.4 ° C. The solution can be applied in the usual way, e.g. by flooding, dipping or spraying. Spray treatment is preferred because of the uniform distribution of the solution over the inner and outer surfaces of the aluminum container.

Ein Teil der Lösung der Vorreinigungsstufe wird kontinuierlich oder in bestimmten zeitlichen Abständen abgezogen und der Abwasserbehandlung zugeführt. Dieser Teil wird in der Regel quantitativ durch ggf. angesäuertes Spülwasser ersetzt.Part of the solution from the pre-cleaning stage is withdrawn continuously or at certain intervals and sent to the wastewater treatment. This part is usually replaced quantitatively by acidified rinsing water.

Im Anschluß an die Vorreinigung erfolgt die alkalische Reinigung. Sie erfolgt bevorzugt mit einer Reinigerlösung, die neben alkalisch reagierenden Bestandteilen einen Komplexbildner und wenigstens ein Tensid mit einer HLB-Zahl von wenigstens 12 enthält und einen pH-Wert von wenigstens 10 aufweist.After pre-cleaning, alkaline cleaning takes place. It is preferably carried out using a cleaning solution which, in addition to alkaline components, contains a complexing agent and at least one surfactant with an HLB number of at least 12 and a pH of at least 10.

In dieser Reinigerlösung kann der alkalisch reagierende Bestandteil Alkali- oder Erdalkaliborat, -carbonat, -hydroxid oder -phosphat sowie Mischungen hiervon sein. Alkalihydroxid und - carbonat sind die bevorzugten Bestandteile. Deren Konzentration muß einerseits ausreichen, um die auf der Behälteroberfläche befindlichen Aluminiumteilchen zu entfernen, darf andererseits jedoch keine übermäßige Ätzung der Aluminiumoberfläche hervorrufen. Im Ergebnis muß ein sauberes glänzendes Aussehen der Oberfläche resultieren. Der pH-Wert, der nach unten mit 10 begrenzt ist, kann je nach Beschaffenheit der Behälteroberfläche bis etwa 13 gehen. Vorzugsweise liegt er im Bereich von 11,5 bis 12,5. Die Konzentration liegt üblicherweise zwischen 0,05 und 10 g/I, vorzugsweise zwischen 0,4 und 3,5 g/I.In this cleaning solution, the alkaline component can be alkali or alkaline earth borate, carbonate, hydroxide or phosphate and mixtures thereof. Alkali hydroxide and carbonate are the preferred ingredients. On the one hand, their concentration must be sufficient to remove the aluminum particles on the container surface, but on the other hand it must not cause excessive etching of the aluminum surface. The result must be a clean, shiny appearance of the surface. The pH value, which is capped at 10, can go up to around 13 depending on the nature of the container surface. It is preferably in the range from 11.5 to 12.5. The concentration is usually between 0.05 and 10 g / l, preferably between 0.4 and 3.5 g / l.

Der Komplexbildner muß in der Reinigerlösung löslich und mit den anderen Bestandteilen verträglich sein. Er muß ferner in der Lage sein, die in der Lösung befindlichen Ionen in dem Maße komplex zu binden, daß die Bildung von störenden Niederschlägen vermieden wird. Als Komplexbildner besonders geeignet sind Zuckersäuren, wie Gluconsäure oder Glucoheptansäure, Zitronensäure, Ethylendiamintetraessigsäure, Weinsäure bzw. Salze dieser Säuren und Natriumtripolyphosphat. Die Konzentration der Komplexbildner liegt üblicherweise im Bereich von 0,01 bis 3 g/I, vorzugsweise im Bereich von 0,05 bis 1 g/I.The complexing agent must be soluble in the cleaning solution and compatible with the other components. He must also be able to complexly bind the ions in the solution to the extent that the formation of troublesome precipitates is avoided. Sugar acids such as gluconic acid or glucoheptanoic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid or salts of these acids and sodium tripolyphosphate are particularly suitable as complexing agents. The concentration of the complexing agents is usually in the range from 0.01 to 3 g / l, preferably in the range from 0.05 to 1 g / l.

Die HLB-Zahl des Tensids ist ein Maß für die Größe und Stärke der hydrophilen Tensidkomponente im Verhältnis zur lipophilen Tensidkomponente (vgl. Römpps Chemie-Lexikon, Franckh'sche Verlagsbuchhandlung, Stuttgart, 8. Auflage, Seite 1715). Durch Wahl von Tensiden mit einer HLB-Zahl von wenigstens 12 und vorzugsweise maximal 15 wird eine wirksame Entfernung von Schmiermitteln und organischen Verunreinigungen, die insbesondere von der Verformung und Glättung der Aluminiumbehälter herrühren, erzielt. Außerdem wird die Bildung von Weißrost inhibiert. Bei Verwendung von Tensiden mit einer HLB-Zahl von über 15 sind in der Regel größere Konzentrationen erforderlich, wenn eine vollständige Reinigung erzielt und eine Wiederabscheidung von Verunreinigungen auf der Behälteroberfläche vermieden werden sollen.The HLB number of the surfactant is a measure of the size and strength of the hydrophilic surfactant component in relation to the lipophilic surfactant component (cf. Römpps Chemie-Lexikon, Franckh'sche Verlagsbuchhandlung, Stuttgart, 8th edition, page 1715). By choosing surfactants with an HLB number of at least 12 and preferably a maximum of 15, effective removal of lubricants and organic contaminants, which result in particular from the deformation and smoothing of the aluminum containers, is achieved. The formation of white rust is also inhibited. When using surfactants with an HLB number of over 15, higher concentrations are usually required if complete cleaning is achieved and impurities are re-deposited on the surface Container surface should be avoided.

Geeignete Tenside sind beispielsweise solche, deren hydrophobe Gruppe von Alkylphenol, geradkettigen oder verzweigtkettigen Alkoholen sowie Propylenglykol/Propylenoxid-Polymerisaten gebildet werden. Der hydrophile Bestandteil kann von Ethylenoxidgruppen, deren Endgruppen gegebenenfalls veräthert oder anderweitig besetzt sind, stammen. Tenside auf Basis alkoxylierter Kohlenwasserstoffe sind besonders geeignet.Suitable surfactants are, for example, those whose hydrophobic group is formed by alkylphenol, straight-chain or branched-chain alcohols and propylene glycol / propylene oxide polymers. The hydrophilic constituent can originate from ethylene oxide groups, the end groups of which may be etherified or otherwise occupied. Surfactants based on alkoxylated hydrocarbons are particularly suitable.

Die vorgenannten Tenside können einzeln oder in Kombination eingesetzt werden. Ihre Konzentration sollte üblicherweise 0,003 bis 5 g/I, vorzugsweise 0,02 bis 1,0 g/I, betragen.The aforementioned surfactants can be used individually or in combination. Their concentration should usually be 0.003 to 5 g / l, preferably 0.02 to 1.0 g / l.

Die Applikation der Reinigerlösung erfolgt wie üblich durch z.B. Fluten, Tauchen oder Spritzen bei Temperaturen von etwa 15 bis 65 C, vorzugsweise 32 bis 54 °C, während einer Zeitdauer, die die Reinheit der Aluminiumoberfläche gewährleistet.The application of the cleaning solution is carried out as usual by e.g. Flooding, dipping or spraying at temperatures of about 15 to 65 ° C, preferably 32 to 54 ° C, for a period of time that ensures the purity of the aluminum surface.

Im Anschluß an die alkalische Reinigung erfolgt eine Spülbehandlung mit wäßriger Lösung, vorzugsweise in mehreren Stufen. Der pH-Wert der Spüllösung sollte unter 7,5, vorzugsweise bei 6,5 bis 7, liegen. Bei höheren pH-Werten kann leicht eine Braunfärbung der Aluminiumbehälter bei Stillstand der Behandlungsanlage im Bereich der Spülzone erfolgen. Die Abschlußspülung erfolgt im allgemeinen mit vollentsalztem Wasser.After the alkaline cleaning, a rinsing treatment with an aqueous solution is carried out, preferably in several stages. The pH of the rinsing solution should be below 7.5, preferably 6.5 to 7. At higher pH values, the aluminum containers can easily turn brown when the treatment system is at a standstill in the area of the rinsing zone. The final rinse is generally carried out with deionized water.

Sofern eine weitere naßchemische Behandlung nicht beabsichtigt ist, werden die Aluminiumbehälter im Anschluß an die Spülbehandlung getrocknet, in der Regel auch lackiert, bedruckt oder anderweitig mit dekorativen Überzügen versehen.If no further wet chemical treatment is intended, the aluminum containers are dried after the rinsing treatment, usually also painted, printed or otherwise provided with decorative coatings.

Das erfindungsgemäße Verfahren ist insbesondere mit Vorteil zur Behandlung von Aluminiumbehältern vor der Bildung von Konversionsüberzügen geeignet. Durch Konversionsüberzüge wird die Beweglichkeit der Behälter (Rotation, Gleitung gegeneinander) beim Durchgang durch die Behandlungsanlage und durch die nachfolgenden Fertigungsstufen stark verbessert und zudem die Korrosionsbeständigkeit erhöht. Derartige Konversionsüberzüge können beispielsweise aus Lösungen auf Basis Schwermetallphosphat oder Titan-, Zirkon- und Hafniumfluorid mit oder ohne zusätzlichen Gehalt an Tannin erzeugt werden. Beispiele für Verfahren zur Bildung derartiger Konversionsüberzüge sind in den amerikanischen Patentschriften 4 017 334, 4 054 466 und 4 338 140 gegeben.The method according to the invention is particularly advantageously suitable for the treatment of aluminum containers before the formation of conversion coatings. Conversion coatings greatly improve the mobility of the containers (rotation, sliding against each other) as they pass through the treatment plant and through the subsequent production stages and also increase the corrosion resistance. Such conversion coatings can be produced, for example, from solutions based on heavy metal phosphate or titanium, zirconium and hafnium fluoride with or without additional tannin content. Examples of methods for forming such conversion coatings are given in U.S. Patents 4,017,334, 4,054,466 and 4,338,140.

Auch im Falle der vorgenannten Erzeugung von Konversionsüberzügen schließt sich üblicherweise die vorerwähnte Trocknung, Lackierung etc. an, je nach Verfahrensart nach einer vorherigen erneuten Spülbehandlung.Also in the case of the aforementioned production of conversion coatings, the aforementioned drying, painting, etc. usually follows, depending on the type of process, after a previous rinsing treatment.

Mit Hilfe der Erfindung gelingt es, erhebliche Spülmittelmengen einzusparen und damit auch die Menge des Abwassers, das einer Aufarbeitung bedarf, erheblich zu reduzieren. In der Regel ist es möglich, den gesamten Bedarf der für die Vorreinigungsstufe erforderlichen Lösung aus der Spülstufe zu decken, so daß sich die Menge des insgesamt aufzuarbeitenden Abwassers entsprechend verringert.With the help of the invention it is possible to save considerable amounts of washing-up liquid and thus also to considerably reduce the amount of waste water which requires processing. As a rule, it is possible to cover the entire requirement of the solution required for the pre-cleaning stage from the rinsing stage, so that the total amount of waste water to be treated is reduced accordingly.

Claims (8)

1. A process for cleaning aluminum containers, comprising the steps of
a) pre-cleaning using an aqueous acidic solution, the pH value of which has been adjusted to from 4 to less than 7,
b) alkaline cleaning, subsequently to step a), and
c) rinsing, subsequently to step b) with aqueous solution, the pH value of which is adjusted to less than 7.5 by introducing at least part of the rinsing solution into step a) and recirculating same.
2. The process according to claim 1, characterized in that in the pre-cleaning step a solution is used, the pH value of which has been adjusted to from 4.5 to 5.5.
3. The process according to claims 1 or 2, characterized in that in the pre-cleaning step a solution containing a surfactant is used.
4. The process according to claim 3, characterized in that in the pre-cleaning step a solution containing a surfactant in an amount of from 0.005 to 5 g/I is used.
5. The process according to claim 3, characterized in that in the pre-cleaning step a solution containing a surfactant in an amount of from 0.1 to 1 g/I is used.
6. The process according to any one or more of claims 1 to 5, characterized in that in the pre-cleaning step a solution is used, the temperature of which has been adjusted to <65.6 ° C.
7. The process according to any one or more of claims 1 to 5, characterized in that in the pre-cleaning step a solution is used, the temperature of which has been adjusted to a value within the range of from 32.2 ° C to 54.4 ° C.
8. The process according to any one or more of claims 1 to 7 as pre-treatment of aluminum containers prior to the application of conversion coatings.
EP87101975A 1986-02-18 1987-02-12 Process for cleaning aluminium containers Expired - Lifetime EP0234425B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87101975T ATE78066T1 (en) 1986-02-18 1987-02-12 METHOD OF CLEANING ALUMINUM CONTAINERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83061086A 1986-02-18 1986-02-18
US830610 1986-02-18

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EP0234425A2 EP0234425A2 (en) 1987-09-02
EP0234425A3 EP0234425A3 (en) 1989-02-15
EP0234425B1 true EP0234425B1 (en) 1992-07-08

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EP (1) EP0234425B1 (en)
JP (1) JP2730891B2 (en)
AT (1) ATE78066T1 (en)
AU (1) AU591231B2 (en)
CA (1) CA1286210C (en)
DE (2) DE3780186D1 (en)
GB (1) GB2187206B (en)

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GB2187206A (en) 1987-09-03
AU591231B2 (en) 1989-11-30
DE3704376A1 (en) 1987-08-20
JP2730891B2 (en) 1998-03-25
ATE78066T1 (en) 1992-07-15
DE3780186D1 (en) 1992-08-13
EP0234425A2 (en) 1987-09-02
GB8703714D0 (en) 1987-03-25
EP0234425A3 (en) 1989-02-15
AU6867887A (en) 1987-08-20
JPS62247090A (en) 1987-10-28
GB2187206B (en) 1990-10-03
CA1286210C (en) 1991-07-16

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