EP1148955A1 - Method for cleaning returnable bottles - Google Patents

Method for cleaning returnable bottles

Info

Publication number
EP1148955A1
EP1148955A1 EP00902629A EP00902629A EP1148955A1 EP 1148955 A1 EP1148955 A1 EP 1148955A1 EP 00902629 A EP00902629 A EP 00902629A EP 00902629 A EP00902629 A EP 00902629A EP 1148955 A1 EP1148955 A1 EP 1148955A1
Authority
EP
European Patent Office
Prior art keywords
cleaning
cleaning solution
bottles
enzyme
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00902629A
Other languages
German (de)
French (fr)
Other versions
EP1148955B1 (en
Inventor
Siegfried Bragulla
Brian Glanville
Andreas Potthoff
Harald Kluschanzoff
Alfred Laufenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab Inc
Original Assignee
Henkel Ecolab GmbH and Co KG
Ecolab Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG, Ecolab Inc filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP1148955A1 publication Critical patent/EP1148955A1/en
Application granted granted Critical
Publication of EP1148955B1 publication Critical patent/EP1148955B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/08—Cleaning containers, e.g. tanks
    • B08B9/20—Cleaning containers, e.g. tanks by using apparatus into or on to which containers, e.g. bottles, jars, cans are brought
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention described below lies in the field of commercial cleaning and relates to an automatic, gentle method for cleaning reusable bottles and other reusable containers which serve to hold food.
  • the reusable containers can consist of a wide variety of materials, in particular glass or plastics, such as polycarbonate (PC), polyvinyl chloride (PVC), polyester (for example polyethylene terephthalate, PET or polyethylene naphthenate, PEN) and polyethylene (PE).
  • PC polycarbonate
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PEN polyethylene naphthenate
  • PE polyethylene
  • Bottles are preferably used for liquids, while cups or cans are preferably used for foods with pasty, gel-like or solid consistency.
  • bottles or bottle cleaning we will only speak of bottles or bottle cleaning in the following, meaning that the other containers to be cleaned in this way or their cleaning are also meant.
  • zones for pre-rinsing, cleaning and post-rinsing there can be several separate zones for pre-rinsing, cleaning and post-rinsing, and depending on the intended use, additional zones, such as an upstream emptying of the bottles, are provided.
  • the contacting of the bottles with the cleaning liquids can take place differently in each zone and is usually designed as a spraying or dipping process.
  • the bottles are first slowly warmed up in the pre-cleaning area, treated in the lye area at a significantly higher temperature and then cooled down again in the subsequent rinsing zones.
  • the division into different baths and zones means that cleaning agents, water and thermal energy are used economically and effectively.
  • This area comprises at least one zone in which the bottles are treated with a cleaning solution at high temperatures of usually about 60 to 90 ° C., depending on the bottle material. Particularly good cleaning effects are achieved when 1 to 3 caustic baths are combined with a subsequent caustic spray zone.
  • a cleaning solution is used as the lye, which contains approx. 1-3% sodium hydroxide as well as additives to sequestering agents, surfactants and other cleaning-active components. Only with such highly alkaline alkalis has it previously been believed that the bottles can be cleaned satisfactorily in a short time.
  • the object of the present invention was to develop an improved method for cleaning bottles, with which the disadvantages of the previously customary methods are avoided as far as possible without having to accept compromises in the cleaning result.
  • the invention therefore relates to a method for cleaning reusable bottles and similar containers which serve to hold food, in which the used bottles are transported in a bottle washing machine through a plurality of cleaning zones, of which at least one zone of pre-rinsing and at least one subsequent zone of treatment serve with a cleaning solution at elevated temperature and at least one further zone of rinsing with water, at least one enzyme being added to the cleaning solution to enhance the cleaning performance.
  • Enzymes from the group of proteases, amylases, cellulases, lipases, oxidoreductases and mixtures of these enzymes are preferably used.
  • the use of proteases, in particular highly alkaline proteases, alone or together with other enzymes is particularly preferred.
  • Another object of the invention is the use of a corresponding solution in a method mentioned above.
  • all those enzymes can be used as enzymes which have a degrading effect on the food residues and impurities to be removed.
  • the above-mentioned enzymes from the group of proteases, amylases, cellulases, glycosidases, lipases and oxidoreductases are particularly preferred.
  • the cleaning process can be specifically adapted to the food residues to be removed.
  • proteases are preferably used to remove protein-containing impurities
  • lipases are used for starch-containing impurities, preferably amylases and for the removal of fatty impurities.
  • the combination of several enzymes for different substrates is recommended if mixed impurities are present.
  • Proteases are therefore primarily used for the preferred application of the method according to the invention in the area of bottles for dairy products, in particular for milk bottles.
  • Particularly preferred is the use of so-called highly alkaline proteases which have an isoelectric point in the range above pH 10 and whose optimum activity lies in the pH range from approximately 9 to approximately 12.
  • This enzyme group includes certain representatives of the serine proteases obtained from bacteria, known as subtilisins, which as a subgroup in scientific literature have been given the common name I-S2.
  • This group includes, for example, the enzymes referred to as Subtilisin 147, Subtilisin 309 and Subtilisin PB92 (see also RJ Siezen et al, Protein Engineering Vol.
  • Highly alkaline proteases are also commercially available as enzyme preparations, for example under the names Savinase ® , Esperase ® , Durazym ® , Maxacal ® , Plurafect ® , Opticlean ® and BLAP ® . In addition to the actual active enzyme, these preparations usually contain large amounts of stabilizing agents and carriers.
  • the enzyme content is usually not given as a percentage by weight, but in a standardized manner in the form of activity units; for the proteases, therefore, the available protein-splitting activity in the respective enzyme preparation or in the enzyme-containing solution.
  • the KNPU Koreano Novo Protease Units
  • the enzyme solution used according to the invention should preferably contain about 0.16 KNPU to about 160 KNPU, in particular about 0.8 KNPU to about 80 KNPU per liter. The range from about 1.6 KNPU to about 16 KNPU per liter of application solution is particularly preferred.
  • the content of the other enzymes is measured in a similar manner: Unit for amylase: MWU (Modified Wohlgemut Unit) Unit for lipase: KLU (Kilo Lipolase Unit
  • the preparation of the cleaning solution used according to the invention is preferably based on the highly concentrated liquid or powdery enzyme preparations which are offered by various manufacturers. The blending agents, auxiliaries or solvents added to these enzyme preparations then also become part of the cleaning solution.
  • the preparations of highly alkaline proteases offered under the name Savinase ®, Maxacal ® and BLAP ® are particularly preferred for the novel process.
  • the finished enzyme-containing cleaning solutions intended to act on the bottles generally have a weakly alkaline pH, which is preferably between about 8 and about 12 and in particular between about 8.5 and about 9.5 (measured at 20 ° C.) .
  • a pH value significantly below the value in the activity maximum of the enzyme is chosen especially when it is important to maintain the activity of the enzyme in the application solution for as long as possible.
  • the pH can be adjusted by methods known per se, for example by using substances with a buffering action or also by a device for automatically metering the necessary amount of alkali.
  • the cleaning solution is to act on the bottles at elevated temperature, with significantly lower temperatures than with the previously known cleaning with highly alkaline solutions being sufficient.
  • the exposure temperatures are preferably between approximately 30 and approximately 70 ° C., in particular between approximately 40 and approximately 55 ° C. Despite these low exposure temperatures, no longer exposure times than with conventional cleaning processes are necessary to achieve a perfect cleaning result.
  • the enzyme-containing cleaning solutions used according to the invention can contain further active ingredients and auxiliaries.
  • surfactants for strengthening the cleaning action are to be mentioned here, whereby in principle surfactants from all known classes can be used.
  • nonionic, cationic and amphoteric surfactants are preferred which in turn have the most important nonionic surfactants.
  • further auxiliaries and additives are enzyme stabilizers, such as soluble calcium salts and borates, compounds with a threshold effect, complexing agents, builders, thickeners, antioxidants, foam inhibitors and preservatives. When choosing all auxiliaries and additives, care must be taken to ensure that there are no interfering interactions with one another and with the enzymes.
  • Suitable nonionic surfactants are in particular the addition products of long-chain alcohols, alkylphenols, amides and carboxylic acids with ethylene oxide (EO), if appropriate together with propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • these include, for example, the addition products of long-chain primary and secondary alcohols with 12 to 18 carbon atoms in the chain, in particular of fatty alcohols and oxoalcohols of this chain length with 1 to 20 mol of EO, and the addition products of fatty acids with 12 to 18 carbon atoms in the chain with preferably 2 to 8 moles of ethylene oxide.
  • the mixed addition products of ethylene and propylene oxide and fatty alcohols having 12 to 18 carbon atoms are particularly preferred, in particular those which contain about 2 mol of EO and about 4 mol of PO in the molecule.
  • the open terminal functional alcohol group can also be closed by an alkyl group. Methyl or butyl is preferably used as the alkyl group.
  • nonionic surfactants examples include alcohol alkoxylates about the fat supplied under the names Dehypon® ® LS24, LS54 Dehypon® ®, Eumulgin ® 05, Dehydrol® ® LT8, Dehydrol® ® LT8, Dehydrol® ® LT 6, Dehydrol® ® LS6 and Dehydrol® ® LT104 by Henkel KGaA .
  • Other suitable nonionic surfactants are the esters of fatty acids with 6 to 12 carbon atoms and polyols, especially carbohydrates, eg glucose. If nonionic surfactants are present in the cleaning solutions used according to the invention, their content there is preferably about 0.001 to about 0.08% by weight, in particular about 0.01 to about 0.05% by weight, based on the ready-to-use solution.
  • Suitable cationic surfactants are, in particular, aliphatic and heterocyclic quaternary ammonium compounds and quaternary phosphonium compounds, which am - o -
  • quaternary center have at least one long-chain C 8 to C 18 alkyl radical.
  • cationic surfactants are cocoalkyl-benzyl-dimethylammonium chloride, dioctyl-dimethylammonium chloride and tributyl-tetradecylphosphonium chloride.
  • Suitable amphoteric surfactants are, in particular, C ⁇ to cis fatty acid amide derivatives with a betaine structure, in particular derivatives of glycine, for example cocoalkyldimethylammonium betaine.
  • Cationic or amphoteric surfactants are preferably used in amounts of not more than 0.08% by weight, in particular between 0.001 and 0.02% by weight, in the cleaning solution.
  • Suitable compounds with a threshold effect are polyphosphates, phosphonic acids and polycarboxylates.
  • Suitable polyphosphates are in particular orthophosphate, pyrophosphate, tripolyphosphate, tetrapolyphosphate, hexametaphosphate.
  • Suitable phosphonic acids are primarily nitrilotrimethylenephosphonic acid, hydroxyethane diphosphonic acid, phosphonobutane tricarboxylic acid and other derivatives of phosphonic acid.
  • Suitable polycarboxylates preferably come from the class of polyacrylates, polysuccinates, polyasparaginates or other salts of polyorganic acids.
  • Suitable builders are the polyphosphates, phosphonates, gluconates, citrates, EDTA, NTA and other complexing agents suitable as builders. Compounds with a threshold effect are preferably used in amounts of about 0.002 to about 0.05% by weight, in particular about 0.004 to about 0.02% by weight, based on the finished application solution.
  • the individual components of the solution can in principle be metered separately and dissolved in the water. It is more expedient, however, to start from prefabricated concentrates which contain several or preferably all of the constituents in the correct mixing ratio, so that only a few metering steps or only one are required. Liquid concentrates are particularly easy to dose, but concentrated formulations also come in the form of powder, tablets or WO 00/45969 _ g _ PCT / EP00 / 0 ⁇ 532
  • Solubilizers such as cumene sulfonate, xylene sulfonate and octyl sulfonate can be considered as additional constituents of liquid concentrates, but other conventional solubilizers can of course also be used.
  • the content of solubilizers is selected as required and is preferably about 1 to about 10% by weight, in particular about 2 to about 5% by weight, based on the concentrate as a whole.
  • Liquid concentrates can also contain large amounts of organic solvents, especially polyols, such as propylene glycol or glycerin.
  • a general formulation for a liquid and a solid detergent concentrate is given:
  • Liquid cleaning concentrate
  • Enzyme in particular protease 1 to 10% by weight, preferably 3 to 6% by weight
  • Glycerol 5 to 20% by weight, preferably 5 to 8% by weight nonionic surfactant 2 to 40% by weight, preferably 5 to 25% by weight
  • Quaternary ammonium compounds e.g. Dioctyldimethylammonium chloride 1 to 40% by weight, preferably 2 to 5% by weight
  • Enzyme in particular protease 1 to 10% by weight, preferably 3 to 6% by weight
  • Nonionic surfactant 2 to 40% by weight, preferably 5 to 25% by weight
  • Quaternary ammonium compound eg dioctyldimethylammonium chloride 1 to 40% by weight, preferably 2 to 10% by weight
  • Potassium triphosphate 1 to 30% by weight, preferably 3 to 10% by weight
  • Phosphonate 0.5 to 5% by weight, preferably 1 to 3% by weight
  • the cleaning agent concentrates are usually added to the water in amounts of about 0.05 to about 0.5% by weight, preferably 0.1 to 0.2% by weight, in order to obtain a ready-to-use cleaning solution for the process according to the invention.
  • the cleaning test was carried out in a one-end bottle washer, which is often found in practice and is sold by machine manufacturers such as Krones, KHS or Simonazzi.
  • the treatment sequence in the machine included two pre-soak stages, an alkali softening zone, two alkali sprayings, a post-alkali, two warm water baths with spray for rinsing out the cleaning solution and a cold water zone with fresh water spray.
  • the aim of the cleaning attempt was to clean heavily soiled glass milk bubbles, which the consumer returned to the milk filling area as normal return material, within a caustic treatment time (caustic soak, caustic spray and post-caustic) of approx. 8 minutes.
  • the test was carried out with 50,000 dirty bottles in a conventional cleaning solution.
  • the liquor contained an aqueous solution of about 2% NaOH, 0.02% sodium gluconate, 0.02% sodium citrate, 0.04% Dehypon LT 104 ®, 0.02% NTA in detail.
  • the total exposure time including dipping and spraying was approx. 8 minutes and the exposure temperature was around 85 ° C. After visual inspection, 258 bottles out of 50,000 bottles were not completely cleaned.
  • the new cleaning solution contained in particular an aqueous solution of approx. 0.005% Esperase, 0.036% butylglycol, 0.020 Dehypon ® LT 104.
  • the total contact time was also approx. 8 minutes and the contact temperature was around 50 ° C.
  • 26 bottles with residues were identified by visual inspection after the cleaning process.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning In General (AREA)

Abstract

The novel method is used to clean returnable bottles and similar containers in the food industry. The inventive method uses an enzymatic solution instead of a high alkaline solution in conventional bottle washing machines during the cleaning process. The cleaning results are at least as good without incurring any increase in the duration of cleaning. Bottle corrosion and waste water pollution are, however, substantially reduced.

Description

„Verfahren zur Reinigung von Mehrwegflaschen" "Process for cleaning reusable bottles"
Die im folgenden beschriebene Erfindung liegt auf dem Gebiet der gewerblichen Reinigung und betrifft ein automatisches schonendes Verfahren zur Reinigung von Mehrwegflaschen und anderen Mehrwegbehältern, die der Aufnahme von Lebensmittel dienen.The invention described below lies in the field of commercial cleaning and relates to an automatic, gentle method for cleaning reusable bottles and other reusable containers which serve to hold food.
Zahlreiche Lebensmittel, insbesondere Molkereiprodukte und Getränke, werden in zunehmendem Maße in Mehrwegverpackungen angeboten, die nach Entleerung vom Kunden zurückgegeben werden und erneut als Verpackung für diese Lebensmittel dienen können. Beispiele für so verpackte Lebensmittel sind Milch, Kakao, Sahne, Joghurt, Milchmixgetränke, Mineralwasser, Fruchtsäfte, Bier, Limonaden, Softdrinks und andere Mixgetränke. Die Mehrwegbehälter können aus verschiedensten Materialien bestehen, insbesondere aus Glas oder aus Kunststoffen, wie Poly- carbonat (PC), Polyvinylchlorid (PVC), Polyester (beispielsweise Polyethylen- terephthalat, PET oder Polyethylennaphthenat, PEN) und Polyethylen (PE). Die Behälter können in ihrer Form den verschiedensten Anwendungszwecken angepaßt sein. So werden für Flüssigkeiten vorzugsweise Flaschen verwendet, während für Lebensmittel mit pastöser, gelartiger oder fester Konsistenz vorzugsweise Becher oder Dosen verwendet werden. Der Einfachheit halber wird im folgenden nur von Flaschen oder Flaschenreinigung gesprochen, wobei sinngemäß auch die anderen in dieser Weise zu reinigenden Behälter bzw. deren Reinigung gemeint sind.Numerous foods, in particular dairy products and beverages, are increasingly being offered in reusable packaging, which the customer returns after emptying and can again be used as packaging for these foods. Examples of foods packaged in this way are milk, cocoa, cream, yoghurt, mixed milk drinks, mineral water, fruit juices, beer, lemonades, soft drinks and other mixed drinks. The reusable containers can consist of a wide variety of materials, in particular glass or plastics, such as polycarbonate (PC), polyvinyl chloride (PVC), polyester (for example polyethylene terephthalate, PET or polyethylene naphthenate, PEN) and polyethylene (PE). The shape of the containers can be adapted to a wide variety of applications. Bottles are preferably used for liquids, while cups or cans are preferably used for foods with pasty, gel-like or solid consistency. For the sake of simplicity, we will only speak of bottles or bottle cleaning in the following, meaning that the other containers to be cleaned in this way or their cleaning are also meant.
Es ist selbstverständlich, daß die zurückgegebenen bereits benutzten Flaschen vor der Wiederverwendung in hygienisch einwandfreier Weise gereinigt werden müssen. Üblicherweise werden im Gewerbe für diesen Zweck vollautomatische Reinigungsmaschinen eingesetzt, in denen die Flaschen durch mehrere Reinigungszonen transportiert werden. Je nach Art der Behälter und der verwendeten Lebensmittel kommen hier unterschiedliche Maschinenkonstruktionen in Betracht. In der Regel ist in den Maschinen wenigstens eine Zone zur Vorspülung vorhanden, in wenigstens einer weiteren darauf folgenden Zone wird eine Behandlung mit einer Reinigungslösung bei erhöhter Temperatur vorgenommen und schließlich ist wenigstens eine weitere Zone vorgesehen ist, in der die Flaschen mit Wasser gespült werden. Die Vorspülung wird häufig auch als Vorweiche und die Zone, in der die Behandlung mit der Reinigungslösung stattfindet, als Laugenzone bezeichnet. Sowohl für die Vorspülung, die Reinigung als auch die Nachspülung können mehrere getrennte Zonen vorhanden sein und je nach Verwendungszweck sind weitere Zonen, wie beispielsweise eine vorgeschaltete Resteentleerung der Flaschen vorgesehen. Die Kontaktie- rung der Flaschen mit den Reinigungsflüssigkeiten kann in jeder Zone anders erfolgen und ist meist als Spritz- oder Tauchvorgang ausgebildet. Üblicherweise werden die Flaschen beim Durchlaufen der Anlage im Vorreinigungsbereich zunächst langsam erwärmt, im Laugenbereich bei deutlich erhöhter Temperatur behandelt und dann in den folgenden Nachspülzonen wieder abgekühlt. Durch die Einteilung in unterschiedliche Bäder und Zonen werden Reinigungsmittel, Wasser und Wärmeenergie wirtschaftlich und effektiv genutzt.It goes without saying that the returned bottles already used must be cleaned in a hygienically correct manner before reuse. Fully automatic cleaning machines are usually used for this purpose in trade, in which the bottles are transported through several cleaning zones. Depending on the type of container and the food used, different machine designs can be considered. Usually is at least one zone for pre-rinsing is present in the machines, treatment with a cleaning solution at elevated temperature is carried out in at least one further zone, and finally at least one further zone is provided in which the bottles are rinsed with water. The pre-rinse is often referred to as the pre-soak and the zone in which the treatment with the cleaning solution takes place is known as the lye zone. There can be several separate zones for pre-rinsing, cleaning and post-rinsing, and depending on the intended use, additional zones, such as an upstream emptying of the bottles, are provided. The contacting of the bottles with the cleaning liquids can take place differently in each zone and is usually designed as a spraying or dipping process. Usually, the bottles are first slowly warmed up in the pre-cleaning area, treated in the lye area at a significantly higher temperature and then cooled down again in the subsequent rinsing zones. The division into different baths and zones means that cleaning agents, water and thermal energy are used economically and effectively.
Nachdem lose anhaftende Lebensmittelreste und Verunreinigungen in der Vorspül- zone entfernt worden sind, findet die eigentliche Reinigung in der Laugenzone statt. Dieser Bereich umfaßt wenigstens eine Zone, in der die Flaschen in Abhängigkeit von dem Flaschenmaterial mit einer Reinigungslösung bei hohen Temperaturen von üblicherweise etwa 60 bis 90 °C behandelt werden. Besonders gute Reinigungseffekte werden erzielt, wenn 1 bis 3 Laugenbäder mit einer darauf folgenden Laugen- spritzzone kombiniert werden. Als Lauge wird bei den herkömmlichen Reinigungsverfahren eine Reinigungslösung verwendet, die ca. 1 - 3 % Natriumhydroxid sowie Zusätze an Sequestriermitteln, Tensiden sowie anderen reinigungsaktiven Komponenten enthält. Nur mit derart hochalkalischen Laugen glaubte man bisher, in kurzer Zeit eine zufriedenstellende Reinigung der Flaschen erreichen zu können. Dabei war man sich der Nachteile bei der Anwendung dieser Reinigungslösungen durchaus bewußt. So führte die Verwendung starker Alkalilauge zu einer hohen Belastung der Kläranlagen, die weiter dadurch gesteigert wurde, daß in diesen stark alkalischen Laugen zum Teil nur solche Hilfssubstanzen verwendet werden konnten, die biologisch schwer abbaubar waren. Zudem wurden unter den extremen Bedingungen die Oberflächen von Glas- und verschiedenen Kunststoffflaschen angegriffen, so daß die Flaschen bald ein unansehnliches Aussehen bekamen und in vielen Fällen auch sehr früh aus dem Kreislauf ausgeschleust werden mußten. Die Verseifung fetthaltiger Rückstände führte häufig zu Schaumproblemen. Als Gegenmaßnahme müssen Entschäumer eingesetzt werden, die aufgrund kritischen Ausspülverhaltens zu einer Verunreinigung des abzufüllenden Lebensmittels führen können. Schließlich war mit der Verwendung der Alkalilaugen ein nicht zu unterschätzendes Verätzungsrisiko für das Bedienungspersonal verbunden.After loosely adhering food residues and impurities have been removed in the pre-rinse zone, the actual cleaning takes place in the lye zone. This area comprises at least one zone in which the bottles are treated with a cleaning solution at high temperatures of usually about 60 to 90 ° C., depending on the bottle material. Particularly good cleaning effects are achieved when 1 to 3 caustic baths are combined with a subsequent caustic spray zone. In the conventional cleaning processes, a cleaning solution is used as the lye, which contains approx. 1-3% sodium hydroxide as well as additives to sequestering agents, surfactants and other cleaning-active components. Only with such highly alkaline alkalis has it previously been believed that the bottles can be cleaned satisfactorily in a short time. The disadvantages of using these cleaning solutions were well known. The use of strong alkali lye resulted in a high load on the sewage treatment plants, which was further increased by the fact that they were strongly alkaline Some of the bases could only be used with auxiliary substances that were difficult to biodegrade. In addition, the surfaces of glass and various plastic bottles were attacked under the extreme conditions, so that the bottles soon got an unsightly appearance and in many cases had to be removed from the cycle very early. The saponification of fatty residues often led to foam problems. As a countermeasure, defoamers must be used, which can lead to contamination of the food to be filled due to critical rinsing behavior. Finally, the use of the alkali eyes was associated with a risk of chemical burns, which should not be underestimated, for the operating personnel.
Ausgehend von diesen Beobachtungen lag der vorliegenden Erfindung die Aufgabe zugrunde, ein verbessertes Verfahren zur Reinigung von Flaschen zu entwickeln, mit dem die Nachteile der bisher üblichen Verfahren möglichst weitgehend vermieden werden, ohne Abstriche beim Reinigungsergebnis hinnehmen zu müssen.Based on these observations, the object of the present invention was to develop an improved method for cleaning bottles, with which the disadvantages of the previously customary methods are avoided as far as possible without having to accept compromises in the cleaning result.
Überraschenderweise wurde gefunden, daß man zu einem derartigen Verfahren gelangt, wenn man in der Reinigungszone eine enzymhaltige Reinigungslösung verwendet.Surprisingly, it was found that such a process can be achieved if an enzyme-containing cleaning solution is used in the cleaning zone.
Gegenstand der Erfindung ist daher ein Verfahren zur Reinigung von Mehrwegflaschen und ähnlichen Behältern, die der Aufnahme von Lebensmittel dienen, bei dem die gebrauchten Flaschen in einer Flaschenwaschmaschine durch mehrere Reinigungszonen transportiert werden, von denen wenigstens eine Zone der Vorspülung, wenigstens eine folgende Zone der Behandlung mit einer Reinigungslösung bei erhöhter Temperatur und wenigstens eine weitere Zone der Nachspülung mit Wasser dienen, wobei der Reinigungslösung wenigstens ein Enzym zur Verstärkung der Reinigungsleistung zugesetzt wird. Vorzugsweise werden Enzyme aus der Gruppe Pro- teasen, Amylasen, Cellulasen, Lipasen, Oxidoreduktasen und Gemische dieser Enzyme eingesetzt. Besonders bevorzugt ist die Verwendung von Proteasen, insbesondere hochalkalischen Proteasen allein oder zusammen mit anderen Enzymen. Ein weiterer Gegenstand der Erfindung ist die Verwendung einer entsprechenden Lösung in einem vorgenannten Verfahren.The invention therefore relates to a method for cleaning reusable bottles and similar containers which serve to hold food, in which the used bottles are transported in a bottle washing machine through a plurality of cleaning zones, of which at least one zone of pre-rinsing and at least one subsequent zone of treatment serve with a cleaning solution at elevated temperature and at least one further zone of rinsing with water, at least one enzyme being added to the cleaning solution to enhance the cleaning performance. Enzymes from the group of proteases, amylases, cellulases, lipases, oxidoreductases and mixtures of these enzymes are preferably used. The use of proteases, in particular highly alkaline proteases, alone or together with other enzymes is particularly preferred. Another object of the invention is the use of a corresponding solution in a method mentioned above.
Mit dem neuen Verfahren ist es überraschenderweise möglich, in ähnlich kurzen Zeiten wie mit den herkömmlichen hochalkalischen Reinigungslaugen ein zumindest gleichwertiges Reinigungsergebnis bei deutlich niedrigeren Temperaturen und deutlich geringeren pH-Werten zu erreichen. In vielen Fällen wird trotz niedrigerer Wirk- stoffkonzentration in der Reinigungslauge sogar ein deutlich besseres Reinigungsergebnis als mit herkömmlichen hochalkalischen Reinigungslaugen erzielt. Durch die Möglichkeit, mit geringeren Konzentrationen an Reinigungswirkstoffen zu arbeiten und biologisch abbaubare Wirkstoffe zu wählen, ist das neue Verfahren besonders umweltverträglich. Die Korrosion der Flaschenoberflächen ist verschwindend gering und durch die niedrigen Arbeitstemperaturen wird zudem noch Energie eingespart.With the new method it is surprisingly possible to achieve an at least equivalent cleaning result at significantly lower temperatures and significantly lower pH values in similarly short times as with the conventional highly alkaline cleaning lyes. In many cases, despite the lower active substance concentration in the cleaning solution, a significantly better cleaning result is achieved than with conventional, highly alkaline cleaning solutions. The possibility of working with lower concentrations of cleaning agents and choosing biodegradable agents makes the new process particularly environmentally friendly. The corrosion of the bottle surfaces is negligible and the low working temperatures also save energy.
Als Enzyme lassen sich erfindungsgemäß all diejenigen Enzyme einsetzen, die eine abbauende Wirkung auf die zu entfernenden Lebensmittelreste und Verunreinigungen haben. Besonders bevorzugt werden die oben genannten Enzyme aus der Gruppe Proteasen, Amylasen, Cellulasen, Glykosidasen, Lipasen und Oxidoredukta- sen. Durch die Wahl verschiedener Enzyme kann das Reinigungsverfahren den jeweils zu entfernenden Lebensmittelresten spezifisch angepaßt werden. So werden zur Entfernung eiweißhaltiger Verunreinigungen vorzugsweise Proteasen eingesetzt, während für stärkehaltige Verunreinigungen, vorzugsweise Amylasen sowie für die Entfernung fetthaltiger Verunreinigungen Lipasen eingesetzt werden. Die Kombination mehrerer Enzyme für unterschiedliche Substrate empfiehlt sich bei Vorliegen gemischter Verunreinigungen. Für die bevorzugte Anwendung des erfindungsgemäßen Verfahrens im Bereich von Flaschen für Molkereiprodukte, insbesondere für Milchflaschen, werden deshalb in erster Linie Proteasen eingesetzt. Besonders bevorzugt ist die Verwendung sogenannter hochalkalischer Proteasen, die einen isoelektrischen Punkt im Bereich oberhalb von pH 10 aufweisen und deren Aktivitätsoptimum im pH-Bereich von etwa 9 bis etwa 12 liegt. Zu den wichtigsten Vertretern die- ser Enzymgruppe gehören bestimmte Vertreter der aus Bakterien gewonnenen, als Subtilisine bezeichneten Serinproteasen, die als Untergruppe in der wissenschaftlichen Literatur die gemeinsame Bezeichnung I-S2 erhalten haben. Zu dieser Gruppe zählen beispielsweise die als Subtilisin 147, Subtilisin 309 und Subtilisin PB92 bezeichneten Enzyme (siehe auch R. J. Siezen et al, Protein Engineering Vol. 4, No 7, 719 - 737 (1991)). Hochalkalische Proteasen sind auch als Enzymzubereitungen im Handel erhältlich, beispielsweise unter den Bezeichnungen Savinase®, Esperase®, Durazym®, Maxacal®, Plurafect®, Opticlean® und BLAP®. Diese Zubereitungen enthalten neben dem eigentlichen aktiven Enzym in der Regel größere Mengen an Stabilisierungsmitteln und Trägerstoffen.According to the invention, all those enzymes can be used as enzymes which have a degrading effect on the food residues and impurities to be removed. The above-mentioned enzymes from the group of proteases, amylases, cellulases, glycosidases, lipases and oxidoreductases are particularly preferred. By selecting different enzymes, the cleaning process can be specifically adapted to the food residues to be removed. For example, proteases are preferably used to remove protein-containing impurities, while lipases are used for starch-containing impurities, preferably amylases and for the removal of fatty impurities. The combination of several enzymes for different substrates is recommended if mixed impurities are present. Proteases are therefore primarily used for the preferred application of the method according to the invention in the area of bottles for dairy products, in particular for milk bottles. Particularly preferred is the use of so-called highly alkaline proteases which have an isoelectric point in the range above pH 10 and whose optimum activity lies in the pH range from approximately 9 to approximately 12. To the most important representatives This enzyme group includes certain representatives of the serine proteases obtained from bacteria, known as subtilisins, which as a subgroup in scientific literature have been given the common name I-S2. This group includes, for example, the enzymes referred to as Subtilisin 147, Subtilisin 309 and Subtilisin PB92 (see also RJ Siezen et al, Protein Engineering Vol. 4, No 7, 719-737 (1991)). Highly alkaline proteases are also commercially available as enzyme preparations, for example under the names Savinase ® , Esperase ® , Durazym ® , Maxacal ® , Plurafect ® , Opticlean ® and BLAP ® . In addition to the actual active enzyme, these preparations usually contain large amounts of stabilizing agents and carriers.
Der Enzymgehalt wird üblicherweise nicht als Gewichtsprozent, sondern in standardisierter Weise in Form von Aktivitätseinheiten angegeben; für die Proteasen also die verfügbare proteinspaltende Aktivität im jeweiligen Enzympräparat bzw. in der en- zymhaltigen Lösung. Im folgenden wird für Proteasen die von der Firma Novo eingeführten Einheit KNPU (Kilo Novo Protease Units) verwendet; andere Einheiten erfordern gegebenenfalls eine entsprechende Umrechnung. Im Fall von Proteasen soll die erfindungsgemäß verwendete Enzymlösung vorzugsweise etwa 0,16 KNPU bis etwa 160 KNPU, insbesondere etwa 0,8 KNPU bis etwa 80 KNPU pro Liter enthalten. Besonders bevorzugt ist der Bereich von etwa 1 ,6 KNPU bis etwa 16 KNPU pro Liter Anwendungslösung. In ähnlicher Weise wird der Gehalt der anderen Enzyme in folgenden Einheiten gemessen: Einheit für Amylase: MWU (Modified Wohlgemut Unit) Einheit für Lipase: KLU (Kilo Lipolase UnitThe enzyme content is usually not given as a percentage by weight, but in a standardized manner in the form of activity units; for the proteases, therefore, the available protein-splitting activity in the respective enzyme preparation or in the enzyme-containing solution. In the following, the KNPU (Kilo Novo Protease Units) introduced by Novo is used for proteases; other units may require a corresponding conversion. In the case of proteases, the enzyme solution used according to the invention should preferably contain about 0.16 KNPU to about 160 KNPU, in particular about 0.8 KNPU to about 80 KNPU per liter. The range from about 1.6 KNPU to about 16 KNPU per liter of application solution is particularly preferred. The content of the other enzymes is measured in a similar manner: Unit for amylase: MWU (Modified Wohlgemut Unit) Unit for lipase: KLU (Kilo Lipolase Unit
Von diesen Enzymen werden vorzugsweise 0,2 bis 100 Einheiten pro Liter Anwendungslösung eingesetzt. Grundsätzlich richtet sich aber in allen Fällen die notwendige Menge an Enzym nach der zu lösenden Reinigungsaufgabe, so daß im Einzelfall die obengenannten Werte ohne weiteres überschritten aber auch unterschritten werden könnnen. Vorzugsweise wird bei der Zubereitung der erfindungsgemäß verwendeten Reinigungslösung von den hochkonzentrierten flüssigen bzw. pulverförmigen Enzympräparaten ausgegangen, die von verschiedenen Herstellern angeboten werden. Die diesen Enzympräparaten beigemischten Verschnittmittel, Hilfsmittel oder Lösungsmittel werden dann ebenfalls Bestandteil der Reinigungslösung. Besonders bevorzugt werden für das erfindungsgemäße Verfahren die unter dem Namen Savinase®, Maxacal® und BLAP® angebotenen Zubereitungen von hochalkalischen Proteasen.Of these enzymes, 0.2 to 100 units per liter of application solution are preferably used. In principle, however, the amount of enzyme required in all cases depends on the cleaning task to be solved, so that in individual cases the above-mentioned values can easily be exceeded or even fallen short of. The preparation of the cleaning solution used according to the invention is preferably based on the highly concentrated liquid or powdery enzyme preparations which are offered by various manufacturers. The blending agents, auxiliaries or solvents added to these enzyme preparations then also become part of the cleaning solution. The preparations of highly alkaline proteases offered under the name Savinase ®, Maxacal ® and BLAP ® are particularly preferred for the novel process.
Die fertigen, zur Einwirkung auf die Flaschen vorgesehenen enzymhaltigen Reinigungslösungen weisen in der Regel einen schwachalkalischen pH-Wert auf, der vorzugsweise zwischen etwa 8 und etwa 12 und insbesondere zwischen etwa 8,5 und etwa 9,5 (gemessen bei 20 °C) liegt. Ein pH-Wert deutlich unterhalb des Wertes im Aktivitätsmaximum des Enzyms wird vor allem dann gewählt, wenn es darauf ankommt, die Aktivität des Enzyms in der Anwendungslösung möglichst lange aufrechtzuerhalten. Der pH-Wert kann durch an sich bekannte Verfahren, beispielsweise durch Verwendung puffernd wirkender Substanzen oder auch durch ein Gerät zur automatischen Dosierung der notwendigen Menge an Alkali eingestellt werden.The finished enzyme-containing cleaning solutions intended to act on the bottles generally have a weakly alkaline pH, which is preferably between about 8 and about 12 and in particular between about 8.5 and about 9.5 (measured at 20 ° C.) . A pH value significantly below the value in the activity maximum of the enzyme is chosen especially when it is important to maintain the activity of the enzyme in the application solution for as long as possible. The pH can be adjusted by methods known per se, for example by using substances with a buffering action or also by a device for automatically metering the necessary amount of alkali.
Im erfindungsgemäßen Verfahren soll die Reinigungslösung bei erhöhter Temperatur auf die Flaschen einwirken, wobei deutlich niedrigere Temperaturen als bei der bisher bekannten Reinigung mit hochalkalischen Lösungen ausreichen. Vorzugsweise liegen die Einwirkungstemperaturen zwischen etwa 30 und etwa 70 °C, insbesondere zwischen etwa 40 und etwa 55 °C. Trotz dieser niedrigen Einwirkungstemperaturen sind keine längeren Einwirkungszeiten als bei herkömmlichen Reinigungsverfahren notwendig, um ein einwandfreies Reinigungsergebnis zu erzielen.In the method according to the invention, the cleaning solution is to act on the bottles at elevated temperature, with significantly lower temperatures than with the previously known cleaning with highly alkaline solutions being sufficient. The exposure temperatures are preferably between approximately 30 and approximately 70 ° C., in particular between approximately 40 and approximately 55 ° C. Despite these low exposure temperatures, no longer exposure times than with conventional cleaning processes are necessary to achieve a perfect cleaning result.
Neben den bereits genannten Bestandteilen können die erfindungsgemäß verwendeten enzymhaltigen Reinigungslösungen weitere Wirkstoffe und Hilfsstoffe enthalten. In erster Linie sind hier Tenside zur Verstärkung der Reinigungswirkung zu nennen, wobei prinzipiell Tenside aus allen bekannten Klassen Verwendung finden können. Bevorzugt werden aber nichtionische, kationische und amphotere Tenside, von denen wiederum die nichtionischen Tenside die größte Bedeutung besitzen. Beispiele für weitere Hilfs- und Zusatzstoffe sind Enzymstabilisatoren, wie lösliche Cal- ciumsalze und Borate, Verbindungen mit Threshold-Effekt, Komplexierungsmittel, Builder, Verdickungsmittel, Antioxidantien, Schauminhibitoren und Konservierungsmittel. Bei der Wahl sämtlicher Hilfs- und Zusatzstoffe ist darauf zu achten, daß keine störenden Wechselwirkungen untereinander und mit den Enzymen auftreten.In addition to the constituents already mentioned, the enzyme-containing cleaning solutions used according to the invention can contain further active ingredients and auxiliaries. Primarily surfactants for strengthening the cleaning action are to be mentioned here, whereby in principle surfactants from all known classes can be used. However, nonionic, cationic and amphoteric surfactants are preferred which in turn have the most important nonionic surfactants. Examples of further auxiliaries and additives are enzyme stabilizers, such as soluble calcium salts and borates, compounds with a threshold effect, complexing agents, builders, thickeners, antioxidants, foam inhibitors and preservatives. When choosing all auxiliaries and additives, care must be taken to ensure that there are no interfering interactions with one another and with the enzymes.
Geeignete nichtionische Tenside sind insbesondere die Additionsprodukte aus langkettigen Alkoholen, Alkylphenolen, Amiden und Carbonsäuren mit Ethylenoxid (EO) gegebenenfalls zusammen mit Propylenoxid (PO). Hierzu zählen beispielsweise die Additionsprodukte von langkettigen primären und sekundären Alkoholen mit 12 bis 18 C-Atomen in der Kette, insbesondere von Fettalkoholen und Oxoalkoholen dieser Kettenlänge mit 1 bis 20 Mol EO und die Additionsprodukte aus Fettsäuren mit 12 bis 18 C-Atomen in der Kette mit vorzugsweise 2 bis 8 Mol Ethylenoxid. Besonders bevorzugt werden die gemischten Additionsprodukte aus Ethylen und Propylenoxid und Fettalkoholen mit 12 bis 18 C-Atomen, insbesondere solche, die etwa 2 Mol EO und etwa 4 Mol PO im Molekül enthalten. Je nach Ausführungsform kann die offene endständige funktionielle Alkoholgruppe auch durch eine Alkylgruppe verschlossen sein. Als Alkylgruppe wird vorzugsweise Methyl- oder Butyl- verwendet. Beispiele geeigneter nichtionischer Tenside sind etwa die unter den Bezeichnungen Dehypon® LS24, Dehypon® LS54, Eumulgin® 05, Dehydol® LT8, Dehydol® LT8, Dehydol® LT6, Dehydol® LS6 und Dehydol® LT104 von der Firma Henkel KGaA angebotenen Fett- alkoholalkoxylate. Weitere geeignete nichtionische Tenside sind die Ester aus Fettsäuren mit 6 bis 12 C-Atomen und Polyolen, insbesondere Kohlenhydraten, z.B. Glukose. Sofern nichtionische Tenside in den erfindungsgemäß verwendeten Reinigungslösungen enthalten sind, beträgt ihr Gehalt dort vorzugsweise etwa 0,001 bis etwa 0,08 Gew.-%, insbesondere etwa 0,01 bis etwa 0,05 Gew.-%, bezogen auf die anwendungsfertige Lösung.Suitable nonionic surfactants are in particular the addition products of long-chain alcohols, alkylphenols, amides and carboxylic acids with ethylene oxide (EO), if appropriate together with propylene oxide (PO). These include, for example, the addition products of long-chain primary and secondary alcohols with 12 to 18 carbon atoms in the chain, in particular of fatty alcohols and oxoalcohols of this chain length with 1 to 20 mol of EO, and the addition products of fatty acids with 12 to 18 carbon atoms in the chain with preferably 2 to 8 moles of ethylene oxide. The mixed addition products of ethylene and propylene oxide and fatty alcohols having 12 to 18 carbon atoms are particularly preferred, in particular those which contain about 2 mol of EO and about 4 mol of PO in the molecule. Depending on the embodiment, the open terminal functional alcohol group can also be closed by an alkyl group. Methyl or butyl is preferably used as the alkyl group. Examples of suitable nonionic surfactants are alcohol alkoxylates about the fat supplied under the names Dehypon® ® LS24, LS54 Dehypon® ®, Eumulgin ® 05, Dehydrol® ® LT8, Dehydrol® ® LT8, Dehydrol® ® LT 6, Dehydrol® ® LS6 and Dehydrol® ® LT104 by Henkel KGaA . Other suitable nonionic surfactants are the esters of fatty acids with 6 to 12 carbon atoms and polyols, especially carbohydrates, eg glucose. If nonionic surfactants are present in the cleaning solutions used according to the invention, their content there is preferably about 0.001 to about 0.08% by weight, in particular about 0.01 to about 0.05% by weight, based on the ready-to-use solution.
Als kationische Tenside eignen sich insbesondere aliphatische und heterocyclische quartäre Ammoniumverbindungen und quartäre Phosphoniumverbindungen, die am - o -Suitable cationic surfactants are, in particular, aliphatic and heterocyclic quaternary ammonium compounds and quaternary phosphonium compounds, which am - o -
quartären Zentrum wenigstens einen langkettigen C8 bis C18-Alkylrest aufweisen. Beispiele derartiger kationischer Tenside sind Kokosalkyl-benzyl-dimethylammoni- umchlorid, Dioctyl-dimethylammoniumchlorid und Tributyl-tetradecylphosphonium- chlorid.quaternary center have at least one long-chain C 8 to C 18 alkyl radical. Examples of such cationic surfactants are cocoalkyl-benzyl-dimethylammonium chloride, dioctyl-dimethylammonium chloride and tributyl-tetradecylphosphonium chloride.
Als amphotere Tenside eignen sich insbesondere Cβ bis Cis-Fettsäureamidderivate mit Betainstruktur, insbesondere Derivate des Glycins, beispielsweise Kokosalkyldi- methylammoniumbetain. Kationische beziehungsweise amphotere Tenside werden in Mengen vorzugsweise nicht über 0,08 Gew.-%, insbesondere zwischen 0,001 und 0,02 Gew.-%, in der Reinigungslösung verwendet.Suitable amphoteric surfactants are, in particular, Cβ to cis fatty acid amide derivatives with a betaine structure, in particular derivatives of glycine, for example cocoalkyldimethylammonium betaine. Cationic or amphoteric surfactants are preferably used in amounts of not more than 0.08% by weight, in particular between 0.001 and 0.02% by weight, in the cleaning solution.
Geeignete Verbindungen mit Threshold-Effekt sind Polyphosphate, Phosphonsäuren und Polycarboxylate. Geeignete Polyphosphate sind insbesondere Orthophosphat, Pyrophosphat, Tripolyphosphat, Tetrapolyphosphat, Hexametaphosphat. Geeignete Phosphonsäuren sind in erster Linie Nitrilotrimethylenphosphonsäure, Hydroxiethan- diphosphonsäure, Phosphonobutantricarbonsäure und weitere Derivate von Phos- phonsäure. Geeignete Polycarboxylate kommen bevorzugt aus der Klasse der Po- lyacrylate, Polysuccinate, Polyasparaginate oder anderen Salzen polyorganischer Säuren. Geeignete Builder sind die bereits genannten Polyphosphate, Phosphato- nate, Gluconate, Citrate, EDTA, NTA sowie andere als Builder geeignete Komplexbildner. Verbindungen mit Threshold-Effekt werden vorzugsweise in Mengen von etwa 0,002 bis etwa 0,05 Gew.-%, insbesondere etwa 0,004 bis etwa 0,02 Gew.-% bezogen auf die fertige Anwendungslösung.Suitable compounds with a threshold effect are polyphosphates, phosphonic acids and polycarboxylates. Suitable polyphosphates are in particular orthophosphate, pyrophosphate, tripolyphosphate, tetrapolyphosphate, hexametaphosphate. Suitable phosphonic acids are primarily nitrilotrimethylenephosphonic acid, hydroxyethane diphosphonic acid, phosphonobutane tricarboxylic acid and other derivatives of phosphonic acid. Suitable polycarboxylates preferably come from the class of polyacrylates, polysuccinates, polyasparaginates or other salts of polyorganic acids. Suitable builders are the polyphosphates, phosphonates, gluconates, citrates, EDTA, NTA and other complexing agents suitable as builders. Compounds with a threshold effect are preferably used in amounts of about 0.002 to about 0.05% by weight, in particular about 0.004 to about 0.02% by weight, based on the finished application solution.
Zur Herstellung der erfindungsgemäß verwendeten Reinigungslösung können die einzelnen Bestandteile der Lösung prinzipiell getrennt dosiert und im Wasser aufgelöst werden. Zweckmäßiger ist es jedoch, von vorgefertigten Konzentraten auszugehen, die mehrere oder vorzugsweise sämtliche Bestandteile im richtigen Mischungsverhältnis enthalten, so daß nur wenige Dosierungsschritte oder nur einer erforderlich sind. Besonders einfach zu dosieren sind flüssige Konzentrate, doch kommen ebenfalls konzentrierte Formulierungen in Form von Pulver, Tabletten oder WO 00/45969 _ g _ PCT/EP00/0Ö532To prepare the cleaning solution used according to the invention, the individual components of the solution can in principle be metered separately and dissolved in the water. It is more expedient, however, to start from prefabricated concentrates which contain several or preferably all of the constituents in the correct mixing ratio, so that only a few metering steps or only one are required. Liquid concentrates are particularly easy to dose, but concentrated formulations also come in the form of powder, tablets or WO 00/45969 _ g _ PCT / EP00 / 0Ö532
Pasten in Betracht. Als zusätzliche Bestandteile von flüssigen Konzentraten kommen Lösungsvermittler, wie Cumolsulfonat, Xyiolsulfonat und Octylsulfonat in Betracht, doch können selbstverständlich auch andere übliche Lösungsvermittler eingesetzt werden. Der Gehalt an Lösungsvermittlern wird nach Bedarf gewählt und beträgt vorzugsweise etwa 1 bis etwa 10 Gew.-%, insbesondere etwa 2 bis etwa 5 Gew.-%, bezogen auf das Konzentrat als Ganzes. Flüssige Konzentrate können weiterhin größere Mengen an organischen Lösungsmitteln, insbesondere Polyolen, wie beispielsweise Propylenglykol oder Glycerin enthalten. Im folgenden wird je eine Rahmenrezeptur für ein flüssiges und ein festes Reinigungsmittelkonzentrat angegeben:Pastes into consideration. Solubilizers such as cumene sulfonate, xylene sulfonate and octyl sulfonate can be considered as additional constituents of liquid concentrates, but other conventional solubilizers can of course also be used. The content of solubilizers is selected as required and is preferably about 1 to about 10% by weight, in particular about 2 to about 5% by weight, based on the concentrate as a whole. Liquid concentrates can also contain large amounts of organic solvents, especially polyols, such as propylene glycol or glycerin. In the following, a general formulation for a liquid and a solid detergent concentrate is given:
Flüssiges Reinigungskonzentrat:Liquid cleaning concentrate:
Enzym, insbesondere Protease 1 bis 10 Gew.-%, vorzugsweise 3 bis 6 Gew.-%Enzyme, in particular protease 1 to 10% by weight, preferably 3 to 6% by weight
Propylenglykol 5 bis 80 Gew.-%, vorzugsweise 20 bis 40 Gew.-%Propylene glycol 5 to 80% by weight, preferably 20 to 40% by weight
Glycerin 5 bis 20 Gew.-%, vorzugsweise 5 bis 8 Gew.-% nichtionisches Tensid 2 bis 40 Gew.-%, vorzugsweise 5 bis 25 Gew.- %Glycerol 5 to 20% by weight, preferably 5 to 8% by weight nonionic surfactant 2 to 40% by weight, preferably 5 to 25% by weight
Enzymstabilisator 1 bis 10 Gew.-%, vorzugsweise 2 bis 5 Gew.-%Enzyme stabilizer 1 to 10% by weight, preferably 2 to 5% by weight
Quartäre Ammoniumverbindungen z.B. Dioctyldimethylammonium- chlorid 1 bis 40 Gew.-%, vorzugsweise 2 bis 5 Gew.-%Quaternary ammonium compounds e.g. Dioctyldimethylammonium chloride 1 to 40% by weight, preferably 2 to 5% by weight
Rest zu 100 % WasserRest 100% water
Festes Reinigungsmittelkonzentrat:Solid detergent concentrate:
Enzym, insbesondere Protease 1 bis 10 Gew.-%, vorzugsweise 3 bis 6 Gew.-%Enzyme, in particular protease 1 to 10% by weight, preferably 3 to 6% by weight
Natrium- und/oderSodium and / or
Kaliumcarbonat 5 bis 50 Gew.-%, vorzugsweise 10 bis 30 Gew.-%Potassium carbonate 5 to 50% by weight, preferably 10 to 30% by weight
Natrium- und/oderSodium and / or
Kaliumbicarbonat 5 bis 50 Gew.-%, vorzugsweise 10 bis 30 Gew.-%Potassium bicarbonate 5 to 50% by weight, preferably 10 to 30% by weight
Nichtionisches Tensid 2 bis 40 Gew.-%, vorzugsweise 5 bis 25 Gew.-%Nonionic surfactant 2 to 40% by weight, preferably 5 to 25% by weight
Quartäre Ammoniumverbindung z.B. Dioctyldimethylammonium- chlorid 1 bis 40 Gew.-%, vorzugsweise 2 bis 10 Gew.-%Quaternary ammonium compound eg dioctyldimethylammonium chloride 1 to 40% by weight, preferably 2 to 10% by weight
Natrium- und/oderSodium and / or
Kaliumtriphosphat 1 bis 30 Gew.-%, vorzugsweise 3 bis 10 Gew.-%Potassium triphosphate 1 to 30% by weight, preferably 3 to 10% by weight
Phosphonat 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-%Phosphonate 0.5 to 5% by weight, preferably 1 to 3% by weight
Üblicherweise werden die Reinigungsmittelkonzentrate dem Wasser in Mengen von etwa 0,05 bis etwa 0,5 Gew.-%, vorzugsweise 0,1 bis 0,2 Gew.-% zugesetzt, um eine anwendungsfertige Reinigungslösung für das erfindungsgemäße Verfahren zu erhalten. The cleaning agent concentrates are usually added to the water in amounts of about 0.05 to about 0.5% by weight, preferably 0.1 to 0.2% by weight, in order to obtain a ready-to-use cleaning solution for the process according to the invention.
B e i s p i e l eB e i s p i e l e
Der Reinigungsversuch wurde in einer Einend-Flaschenreinigungsmaschine durchgeführt, wie sie in der Praxis häufig anzutreffen ist und von Maschinenherstellern wie Krones, KHS oder Simonazzi vertrieben werden. Die Behandlungssequenz in der Maschine beinhaltete zwei Vorweich-Stufen, eine Laugenweichzone, zwei Laugenspritzungen, eine Nachlauge, zwei Warmwasserbäder mit Spritzung zum Ausspülen der Reinigungslösung und eine Kaltwasserzone mit Frischwasserspritzung.The cleaning test was carried out in a one-end bottle washer, which is often found in practice and is sold by machine manufacturers such as Krones, KHS or Simonazzi. The treatment sequence in the machine included two pre-soak stages, an alkali softening zone, two alkali sprayings, a post-alkali, two warm water baths with spray for rinsing out the cleaning solution and a cold water zone with fresh water spray.
Der Reinigungsversuch hatte das Ziel, stark verschmutzte Glasmilchflasen, die als normales Rücklaufgut vom Konsumenten in den Miichabfüllbereich zurückgegeben wurden, innerhalb einer Laugenbehandlungszeit (Laugenweiche, Laugenspritzung und Nachlauge) von ca. 8 Minuten zu reinigen.The aim of the cleaning attempt was to clean heavily soiled glass milk bubbles, which the consumer returned to the milk filling area as normal return material, within a caustic treatment time (caustic soak, caustic spray and post-caustic) of approx. 8 minutes.
Zunächst wurde der Versuch mit 50.000 verschmutzten Flaschen in einer herkömmlichen Reinigungslauge durchgeführt. Die Lauge enthielt im einzelnen eine wäßrige Lösung von ca. 2 % NaOH, 0,02 % Natriumgluconat, 0,02 % Natriumeitrat, 0,04 % Dehypon® LT 104, 0,02 % NTA. Die gesamte Einwirkzeit inklusive Tauchen und Spritzen betrug ca. 8 Minuten und die Einwirktemperatur lag bei etwa 85 °C. Von 50.000 Flaschen wurden nach visueller Kontrolle 258 Flaschen nicht vollständig gereinigt.Initially, the test was carried out with 50,000 dirty bottles in a conventional cleaning solution. The liquor contained an aqueous solution of about 2% NaOH, 0.02% sodium gluconate, 0.02% sodium citrate, 0.04% Dehypon LT 104 ®, 0.02% NTA in detail. The total exposure time including dipping and spraying was approx. 8 minutes and the exposure temperature was around 85 ° C. After visual inspection, 258 bottles out of 50,000 bottles were not completely cleaned.
Im Anschluß an diesen Versuch wurde die gesamte Reinigungslauge abgelassen und ein neuer Ansatz gemacht. Die neue Reinigungslösung enthielt im einzelnen eine wäßrige Lösung von ca. 0,005 % Esperase, 0,036 % Butylglycol, 0,020 Dehypon® LT 104. Die gesamte Einwirkzeit betrug ebenfalls ca. 8 Minuten und die Einwirktemperatur lag bei etwa 50 °C. Von 50.000 verschmutzten Flaschen wurden nach dem Reinigungsvorgang durch visuelle Kontrolle noch 26 Flaschen mit Rückständen identifiziert. Following this experiment, the entire cleaning liquor was drained off and a new approach was made. The new cleaning solution contained in particular an aqueous solution of approx. 0.005% Esperase, 0.036% butylglycol, 0.020 Dehypon ® LT 104. The total contact time was also approx. 8 minutes and the contact temperature was around 50 ° C. Of the 50,000 bottles soiled, 26 bottles with residues were identified by visual inspection after the cleaning process.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Reinigung von Mehrwegflaschen und ähnlichen Behältern, die der Aufnahme von Lebensmitteln dienen, bei dem die gebrauchten Flaschen in einer Flaschenwaschmaschine durch mehrere Reinigungszonen transportiert werden, von denen wenigstens eine Zone der Vorspülung, wenigstens eine folgende Zone der Behandlung mit einer Reinigungslösung bei erhöhter Temperatur und wenigstens eine weitere Zone der Nachspülung mit Wasser dienen, dadurch gekennzeichnet, daß der Reinigungslösung wenigstens ein Enzym zur Verstärkung der Reinigungsleistung zugesetzt wird.1. A method for cleaning reusable bottles and similar containers which serve to hold food, in which the used bottles are transported in a bottle washing machine through several cleaning zones, of which at least one zone of pre-rinsing and at least one subsequent zone of treatment with a cleaning solution elevated temperature and at least one further zone of rinsing with water, characterized in that at least one enzyme is added to the cleaning solution to enhance the cleaning performance.
2. Verfahren nach Anspruch 1 , bei dem die Behandlung der Flaschen mit der Reinigungslösung bei Temperaturen zwischen 30 °C und 70 °C, vorzugsweise zwischen 40 °C und 55 °C erfolgt.2. The method according to claim 1, wherein the treatment of the bottles with the cleaning solution is carried out at temperatures between 30 ° C and 70 ° C, preferably between 40 ° C and 55 ° C.
3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem in der Reinigungslösung ein Enzym aus der Gruppe Proteasen, Amylasen, Cellulasen, Lipasen, Oxidore- duktasen und Gemische dieser Enzyme eingesetzt wird.3. The method according to any one of claims 1 or 2, in which an enzyme from the group of proteases, amylases, cellulases, lipases, oxidoreductases and mixtures of these enzymes is used in the cleaning solution.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem in der Reinigungslösung wenigstens eine Protease eingesetzt wird.4. The method according to any one of claims 1 to 3, in which at least one protease is used in the cleaning solution.
5. Verfahren nach Anspruch 4, bei dem eine hochalkalische Protease, vorzugsweise aus der Gruppe der als Subtilisine bezeichneten Serinproteasen, eingesetzt wird.5. The method according to claim 4, in which a highly alkaline protease, preferably from the group of the serine proteases referred to as subtilisins, is used.
6. Verfahren nach einem der Ansprüche 4 oder 5, bei dem die Reinigungslösung 0, 16 bis 160 KNPU, vorzugsweise 0,8 bis 80 KNPU und insbesondere 1 ,6 bis 16 KNPU an Protease pro Liter enthält. 6. The method according to any one of claims 4 or 5, wherein the cleaning solution contains 0, 16 to 160 KNPU, preferably 0.8 to 80 KNPU and in particular 1, 6 to 16 KNPU of protease per liter.
7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die Reinigungslösung einen pH-Wert im Bereich 8 bis 12, vorzugsweise im Bereich 8,5 bis 9,5 aufweist.7. The method according to any one of claims 1 to 6, wherein the cleaning solution has a pH in the range 8 to 12, preferably in the range 8.5 to 9.5.
8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem die Reinigungslösung weitere Wirkstoffe und Hilfsstoffe aus der Gruppe Tenside, Puffersubstanzen, Enzymstabilisatoren, Verbindungen mit Threshold-Effekt, Komplexierungsmittel, Builder, Verdickungsmittel, Antioxidantien, Schauminhibitoren, Konservierungsmittel und deren Gemische enthält.8. The method according to any one of claims 1 to 7, wherein the cleaning solution contains further active ingredients and auxiliaries from the group of surfactants, buffer substances, enzyme stabilizers, compounds with a threshold effect, complexing agents, builders, thickeners, antioxidants, foam inhibitors, preservatives and mixtures thereof.
9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem die Reinigungslösung aus einem enzymhaltigen Konzentrat durch Auflösen in Wasser hergestellt wird.9. The method according to any one of claims 1 to 8, wherein the cleaning solution is prepared from an enzyme-containing concentrate by dissolving in water.
10. Verwendung einer Enzym enthaltenden wäßrigen Lösung zur Reinigung von Mehrwegflaschen und ähnlichen Behältern, die der Aufnahme von Lebensmitteln dienen, in einer Flaschenwaschmaschine, in der die Flaschen durch mehrere Reinigungszonen transportiert werden. 10. Use of an aqueous solution containing enzyme for cleaning reusable bottles and similar containers which serve to hold food in a bottle washing machine in which the bottles are transported through several cleaning zones.
EP00902629A 1999-02-04 2000-01-25 Method for cleaning returnable bottles Expired - Lifetime EP1148955B1 (en)

Applications Claiming Priority (3)

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DE19904512A DE19904512A1 (en) 1999-02-04 1999-02-04 Method for cleaning refillable bottles
DE19904512 1999-02-04
PCT/EP2000/000532 WO2000045969A1 (en) 1999-02-04 2000-01-25 Method for cleaning returnable bottles

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7125204B2 (en) 2003-10-31 2006-10-24 Finn Corporation Portable pneumatic blower

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10141239C2 (en) * 2001-08-23 2003-12-18 Korn Gmbh Use of liquid, water-thinnable pre-rinsing compositions and methods for applying the same
US7148188B2 (en) * 2002-09-18 2006-12-12 Ecolab Inc. Bottlewash additive comprising an alkyl diphenylene oxide disulfonate
US20040235680A1 (en) * 2002-09-18 2004-11-25 Ecolab Inc. Conveyor lubricant with corrosion inhibition
PL2850167T3 (en) 2012-05-14 2019-04-30 Ecolab Usa Inc Label removal solution for returnable beverage bottles
US9487735B2 (en) 2012-05-14 2016-11-08 Ecolab Usa Inc. Label removal solution for low temperature and low alkaline conditions
WO2014200657A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces xiamenensis
WO2014200658A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from promicromonospora vindobonensis
WO2014200656A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces umbrinus
EP3011020A1 (en) 2013-06-17 2016-04-27 Danisco US Inc. Alpha-amylase from bacillaceae family member
EP3060659B1 (en) 2013-10-03 2019-05-29 Danisco US Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
WO2015050724A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from a subset of exiguobacterium, and methods of use, thereof
EP3071691B1 (en) 2013-11-20 2019-10-23 Danisco US Inc. Variant alpha-amylases having reduced susceptibility to protease cleavage, and methods of use, thereof
DE102015008314A1 (en) 2015-06-30 2017-01-05 Krones Ag Treatment machine for treating containers and / or food with supply of a working medium
PL3417043T3 (en) 2016-02-18 2024-03-25 Ecolab Usa Inc. Solvent application in bottle wash using amidine based formulas
WO2017173190A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods
WO2017173324A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2259201A1 (en) 1972-12-02 1974-06-20 Kali Chemie Ag Cleansers for protein and starch-soiled surfaces - contg protease and amylase enzymes and use for cleaning solid surfaces in food, brewery and dairy inds
DE3205956A1 (en) * 1982-02-19 1983-09-15 Robert 6141 Einhausen Becker Bottle-cleaning device, in which heat is recovered and fresh water saved
DE3377140D1 (en) * 1982-11-26 1988-07-28 Unilever Nv Liquid detergent compositions
DE4014747A1 (en) * 1990-05-08 1991-11-14 Henkel Kgaa CLEANING AGENTS FOR PLASTIC MULTIPLE-WAY CONTAINERS OR PLASTIC-COVERED MULTIPLE-WAY GLASS CONTAINERS AND METHOD FOR THE CLEANING THEREOF
DE4411223A1 (en) 1994-03-31 1995-10-05 Solvay Enzymes Gmbh & Co Kg Use of alkaline proteases in commercial textile washing processes
CA2190349A1 (en) * 1994-06-23 1996-01-04 James William Gordon Dishwashing compositions
US5861366A (en) * 1994-08-31 1999-01-19 Ecolab Inc. Proteolytic enzyme cleaner
US5858117A (en) * 1994-08-31 1999-01-12 Ecolab Inc. Proteolytic enzyme cleaner
DE19717329A1 (en) * 1997-04-24 1998-10-29 Henkel Ecolab Gmbh & Co Ohg Liquid enzyme preparation and its use
DE19838939A1 (en) * 1998-08-27 2000-03-09 Henkel Ecolab Gmbh & Co Ohg Process for cleaning milk heaters
CA2377337A1 (en) * 1999-06-25 2001-01-04 The Penn State Research Foundation Stain removing composition containing particular isolated and pure proteolytic enzymes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0045969A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7125204B2 (en) 2003-10-31 2006-10-24 Finn Corporation Portable pneumatic blower

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AU2439800A (en) 2000-08-25
DE19904512A1 (en) 2000-08-17
DE50009724D1 (en) 2005-04-14
US6530386B1 (en) 2003-03-11
PL350164A1 (en) 2002-11-18
EP1148955B1 (en) 2005-03-09
WO2000045969A1 (en) 2000-08-10

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