EP0599907A1 - Method of determining and controlling the concentration of active substances included for cleaning and disinfection purposes in aqueous cleaning and disinfection-agent solutions - Google Patents

Method of determining and controlling the concentration of active substances included for cleaning and disinfection purposes in aqueous cleaning and disinfection-agent solutions

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Publication number
EP0599907A1
EP0599907A1 EP92917156A EP92917156A EP0599907A1 EP 0599907 A1 EP0599907 A1 EP 0599907A1 EP 92917156 A EP92917156 A EP 92917156A EP 92917156 A EP92917156 A EP 92917156A EP 0599907 A1 EP0599907 A1 EP 0599907A1
Authority
EP
European Patent Office
Prior art keywords
concentration
cleaning
solution
iodine
active ingredient
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.)
Ceased
Application number
EP92917156A
Other languages
German (de)
French (fr)
Inventor
Alfred Laufenberg
Mike Varpins
Alfred Werner-Busse
Friedhelm Siepmann
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 AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0599907A1 publication Critical patent/EP0599907A1/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0018—Controlling processes, i.e. processes to control the operation of the machine characterised by the purpose or target of the control
    • A47L15/0055—Metering or indication of used products, e.g. type or quantity of detergent, rinse aid or salt; for measuring or controlling the product concentration
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/24—Apparatus using programmed or automatic operation
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D11/00—Control of flow ratio
    • G05D11/02—Controlling ratio of two or more flows of fluid or fluent material
    • G05D11/13—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means
    • G05D11/135—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means by sensing at least one property of the mixture
    • G05D11/138—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means by sensing at least one property of the mixture by sensing the concentration of the mixture, e.g. measuring pH value
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/24—Washing or rinsing machines for crockery or tableware with movement of the crockery baskets by conveyors
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/4236—Arrangements to sterilize or disinfect dishes or washing liquids
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L2401/00—Automatic detection in controlling methods of washing or rinsing machines for crockery or tableware, e.g. information provided by sensors entered into controlling devices
    • A47L2401/30—Variation of electrical, magnetical or optical quantities
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L2501/00—Output in controlling method of washing or rinsing machines for crockery or tableware, i.e. quantities or components controlled, or actions performed by the controlling device executing the controlling method
    • A47L2501/07—Consumable products, e.g. detergent, rinse aids or salt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0324—With control of flow by a condition or characteristic of a fluid

Definitions

  • the invention relates to a method for determining the concentration of an active ingredient containing iodine / iodide in aqueous active ingredient solutions, in particular for cleaning or disinfecting containers such as bottles, barrels, kegs, boxes and tanks and / or pipelines in the food processing industry Industry as well as for industrial cleaning in continuous washing systems, the concentration of the active substances in the solution being measured by determining their iodine / iodide content.
  • phase separation In cleaning systems for closed systems (ClP systems) in which the cleaning or disinfection solution is used several times, dilution effects also occur due to mixed phases during the pre-rinsing and post-rinsing.
  • stacking used cleaning solutions which are usually pushed out of the pipelines with fresh water, it is necessary to control the point at which the returning solution is fed into the stacking container and the point at which the concentration of cleaning or disinfecting agent in the Rinsing water is no longer worth collecting, and above all, from which rinsing time the system can be filled with food again without the risk of contamination with cleaning or disinfection chemicals.
  • phase separation This process in CIP cleaning is referred to as "phase separation".
  • the precise measurement of the cleaning agent and disinfectant concentration in the cleaning or disinfecting solution or in the rinse water is of paramount importance.
  • the ClP process is the last process often a disinfection step. In particular, contamination of foods with the frequently toxic disinfectants must be avoided and the post-rinsing process should therefore be monitored particularly carefully.
  • the conductivity measurement is carried out as an ⁇ -line measurement method.
  • the safe implementation of this method requires a relatively high conductance of the active ingredient solution of usually at least 3 to 4 mS, which is only achieved by strongly alkaline or strongly acidic solutions.
  • dosing proportional to the bottle throughput Another common way of dosing active ingredient concentrates is dosing proportional to the bottle throughput. This method is based on the consideration that each bottle with the bottle cell carries a constant amount of cleaning solution out of the bath. However, this amount changes depending on the petrification of the bottle cells, the foam behavior of the solution and the control of the liquid flows between the various baths of industrial bottle cleaning machines. From operational practice it is known that the actual detergent concentration can vary from the target concentration by 50 hours or more in the course of a few days when dosing according to the methods mentioned. Lie technical defects of the dosing device, these can only be recognized and corrected after the elaborate manual concentration determination carried out at intervals of 1 to 5 days. In these cases, concentration fluctuations of up to a factor of 40 occur in operational practice.
  • the invention is therefore based on the object of providing a method of the type mentioned at the outset which operates reliably, precisely, quickly, less susceptibly to faults and continuously. It is also intended to automate the replenishment of the active ingredient enable.
  • the method according to the invention should be able to be used in an integrated cleaning technique called "cleaning in place”. These are large, coherent, fully automatic cleaning systems which automatically clean all storage tank and line systems after each production process. The cleaning processes are monitored by small computers, so that a predetermined optimal hygiene standard is produced again and again. This technology is used in the dairy, brewing and beverage industries.
  • the iodine ion concentration in the solution is measured potentiometrically by means of electrodes which selectively respond to iodine ions and the concentration of the active substance is determined from the measured values obtained, the iodine / iodide concentration in the solution being between 0 , 1 and 1000 ppm.
  • the iodine / iodide concentration in the solution is in the range between 1 and 20 ppm.
  • the method according to the invention is advantageously used to measure the concentration of active substance in the caustic baths and water zones of industrial bottle cleaning machines.
  • the method for measuring the active substance concentration of cleaning or disinfectant solutions is used for ClP processes in the food industry.
  • the method for measuring the active substance concentration in industrial continuous washing systems is used in particular for the cleaning of metal sheets or textiles, the objects to be cleaned, in particular, being dragged out of the active substance baths by part of the active substance solution.
  • the concentration of the active ingredient is preferably determined from the measured potential by means of a calibration curve which has been determined by the measured potentials of at least two different concentrations of the active ingredient in the solution to be monitored. Particularly reliable measured values are obtained since the solution present in practice with the typical impurities of the special cleaning and disinfection process is used for calibration. It has turned out to be advantageous if the measuring points used for the calibration comprise a concentration range between one and two decades.
  • direct potentiometry is advantageous when carrying out the method according to the invention, since it immediately delivers current measured values without great expense. Installation in an automatic metering device is also problem-free.
  • it is expedient to plot the potentials obtained against the logarithm of the concentrations, so that a calibration line is obtained.
  • Another aspect of the invention relates to the dosing / re-dosing of an active substance containing iodine / iodide into an aqueous active substance solution.
  • the metering is controlled by a control device which compares the actual concentration determined according to the invention with a predetermined target concentration.
  • An integrated cleaning technology (“cleaning in place”) can be built up with this dosing method.
  • pre-rinse or rinse water is separated from the aqueous active substance solution (phase separation) in ClP processes by controlling the phase separation by a device which compares the determined concentration of the active substance with a predetermined target concentration and controls valves for phase separation in accordance with the comparison result.
  • An iodide electrode and a common pH electrode were installed as the counter electrode in a flow cup.
  • the cleaning liquor was passed through the cup from a running bottle washing machine.
  • the amplified measurement signals were registered on a recorder.
  • a calibration curve was recorded, in which the potential of the original solution and the solution was measured after increasing the detergent concentration by a factor of 10.
  • the concentration of the detergent in the original solution was determined photometrically.
  • the calibration line was created by plotting the logarithm of the potentials against the concentration.
  • detergents were added in portions during the measurement.
  • the cleaning agent is the commercial product P3-Stabi1on AL liquid, an active ingredient concentrate for bottle cleaning, which is also suitable for removing aluminum foils, labels and capsules.
  • the results obtained are found in Table 1 for a cleaning solution with soiling and in Table 2 for a fresh cleaning solution.
  • Table 1 for a cleaning solution with soiling
  • Table 2 for a fresh cleaning solution.

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Automation & Control Theory (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé pour la détermination de la concentration d'une matière active contenant de l'iode/iodure dans des solutions aqueuses de matières actives utilisées notamment pour le nettoyage ou la désinfection de récipients tels que bouteilles, fûts, tonnelets, caissons et réservoirs et/ou conduites, dans l'industrie de transformation alimentaire ainsi que pour le nettoyage industriel dans des installations de lavage en continu, procédé selon lequel la concentration de la matière active dans la solution est mesurée par l'intermédiaire d'une détermination de sa teneur en iode/iodure. L'invention vise à obtenir un procédé fiable, précis, rapide, fonctionnant en continu sans être sujet à des pannes, tout en permettant une automatisation du dosage ultérieur de la matière active. Le procédé selon l'invention devra en particulier s'insérer dans une technique intégrée de nettoyage dite de "cleaning in place". Ces avantages sont obtenus, conformément à l'invention, grâce au fait qu'on mesure par potentiométrie la concentration en ions iode dans la solution, au moyen d'électrodes répondant sélectivement aux ions iode, et qu'on détermine, à partir des valeurs de mesure obtenues, la concentration en matière active, la concentration en iode/iodure dans la solution étant comprise entre 0,1 et 1000 ppm. En particulier, la concentration en iode/iodure dans la solution est comprise entre 1 et 20 ppm.The invention relates to a method for determining the concentration of an active material containing iodine / iodide in aqueous solutions of active materials used in particular for cleaning or disinfecting containers such as bottles, barrels, kegs, boxes. and tanks and / or pipes, in the food processing industry as well as for industrial cleaning in continuous washing plants, process by which the concentration of the active ingredient in the solution is measured by means of a determination of its iodine / iodide content. The invention aims to obtain a reliable, precise, rapid process, operating continuously without being subject to breakdowns, while allowing automation of the subsequent dosing of the active material. The method according to the invention should in particular be part of an integrated cleaning technique called "cleaning in place". These advantages are obtained, in accordance with the invention, by virtue of the fact that the concentration of iodine ions in the solution is measured by potentiometry, by means of electrodes which respond selectively to iodine ions, and that it is determined from the values of measurement obtained, the concentration of active material, the iodine / iodide concentration in the solution being between 0.1 and 1000 ppm. In particular, the concentration of iodine / iodide in the solution is between 1 and 20 ppm.

Description

Verfahren zum Bestimmen und Regeln der Konzentration von Wirkstoffen zur Reinigung und Desinfektion in wäßrigen Reinigungs- und Desinfektionsmittellδsuπgen Method for determining and regulating the concentration of active ingredients for cleaning and disinfection in aqueous cleaning and disinfectant solutions
Die Erfindung betrifft ein Verfahren zum Bestimmen der Konzentration eines Jod / Jodid enthaltenden Wirkstoffs in wäßrigen Wirkstofflö¬ sungen, die insbesondere zur Reinigung oder Desinfektion von Behäl¬ tern wie Flaschen, Fässern, Kegs, Kästen und Tanks und/oder Rohr¬ leitungen in der lebensmittelverarbeitenden Industrie sowie zur in¬ dustriellen Reinigung in DurchlaufWaschanlagen eingesetzt werden, wobei die Konzentration der Wirkstoffe in der Lösung über eine Be¬ stimmung ihres Jod / Jodid-Gehalts gemessen wird.The invention relates to a method for determining the concentration of an active ingredient containing iodine / iodide in aqueous active ingredient solutions, in particular for cleaning or disinfecting containers such as bottles, barrels, kegs, boxes and tanks and / or pipelines in the food processing industry Industry as well as for industrial cleaning in continuous washing systems, the concentration of the active substances in the solution being measured by determining their iodine / iodide content.
Bei der Verwendung von Reinigungsmitteln in der gewerblichen Wirt¬ schaft ist es aus Umweltschutzgründen und wirtschaftlichen Ge¬ sichtspunkten einerseits erwünscht, eine Überdosierung zu vermeiden. Andererseits führt aber eine Unterdosierung zu einem ungenügenden Reinigungsergebnis. Eine Lösung des Problems wird erschwert, wenn die zu reinigenden Gegenstände kontinuierlich ein Reinigungs- oder Desinfektionsbad durchlaufen, wie dies häufig bei der gewerblichen Reinigung, z. B. bei der Flaschen-, Fässer-, Keg-, Behälterreinigung und der gewerblichen Reinigung von Blechen oder Textilien der Fall ist. Mit den gereinigten oder desinfizierten Gegenständen wird näm¬ lich Reinigungs- oder Desinfektionsmittel aus dem Bad ausgeschleppt, so daß eine kontinuierliche oder diskontinuierliche Auffüllung des Reinigungs- oder Desinfektioπsbades mit Frischwasser vorgenommen wird. Die sich allmählich verringernde Konzentration an Reinigungs¬ oder Desinfektionsmittel wird gemessen und bei Bedarf nachdosiert.When using cleaning agents in the commercial economy, it is desirable, on the one hand, for environmental protection and economic reasons to avoid overdosing. On the other hand, underdosing leads to an insufficient cleaning result. A solution to the problem is made more difficult if the objects to be cleaned continuously run through a cleaning or disinfection bath, as is often the case with commercial ones Cleaning, e.g. B. in the bottle, barrel, keg, container cleaning and commercial cleaning of sheets or textiles is the case. With the cleaned or disinfected objects, cleaning agents or disinfectants are towed out of the bath, so that the cleaning or disinfection bath is filled continuously or discontinuously with fresh water. The gradually decreasing concentration of cleaning or disinfectant is measured and replenished if necessary.
Bei Reinigungssystemen für geschlossene Anlagen (ClP-Systeme), bei denen die Reinigungs- oder Desinfektionslösung mehrfach verwendet wird, treten durch Mischphasen bei der Vor- und Nachspülung eben¬ falls Verdünnungseffekte auf. Zusätzlich muß bei der Stapelung ge¬ brauchter Reinigungslösungen, die üblicherweise mit Frischwasser aus den Rohrleitungen ausgeschoben werden, gesteuert werden, bis zu welchem Zeitpunkt die rückkehrende Lösung in den Stapelbehälter ge¬ führt wird und ab wann die Konzentration an Reinigungs- oder Desin¬ fektionsmittel im Nachspülwasser das Auffangen nicht mehr lohnt, und vor allem, ab welcher Nachspüldauer die Anlage erneut mit Lebens¬ mitteln befällt werden kann, ohne daß eine Kontamination mit Reini¬ gungs- oder Desinfektionschemikalien befürchtet werden muß. Dieses Verfahren bei der CIP-Reiπigung wird als "Phasentrennuπg" bezeich¬ net.In cleaning systems for closed systems (ClP systems) in which the cleaning or disinfection solution is used several times, dilution effects also occur due to mixed phases during the pre-rinsing and post-rinsing. In addition, when stacking used cleaning solutions, which are usually pushed out of the pipelines with fresh water, it is necessary to control the point at which the returning solution is fed into the stacking container and the point at which the concentration of cleaning or disinfecting agent in the Rinsing water is no longer worth collecting, and above all, from which rinsing time the system can be filled with food again without the risk of contamination with cleaning or disinfection chemicals. This process in CIP cleaning is referred to as "phase separation".
Bei diesen Betriebsweisen kommt der präzisen Messung der Reinigungs¬ und Desinfektionsmittelkonzentration in der Reinigungs- oder Desin¬ fektionslösung oder in dem Nachspülwasser eine überragende Bedeutung zu. Bei der Reinigung sind die Wirkstoffkonzentrationen aus den oben genannten Gründen in engen Grenzen zu halten. Z. B. führen zu hohe Konzentrationen bei der Reinigung wiederbefü11barer PET-Flaschen (PET = Polyethylenterephtalat) zu Spannungsrißkorrosion, bei zu niedrigen Konzentrationen werden die Flaschen ebenfalls angegriffen und das Reinigungsergebnis ist ungenügend. Im ClP-Prozess ist der letzte Vorgang häufig ein Desinfektionsschritt. Besonders die Kon¬ tamination von Lebensmitteln mit den häufig toxischen Desinfekti¬ onsmitteln ist zu vermeiden und der Nachspülprozess daher besonders sorgfältig zu überwachen.In these operating modes, the precise measurement of the cleaning agent and disinfectant concentration in the cleaning or disinfecting solution or in the rinse water is of paramount importance. When cleaning, the active substance concentrations are to be kept within narrow limits for the reasons mentioned above. For example, concentrations that are too high when cleaning refillable PET bottles (PET = polyethylene terephthalate) lead to stress corrosion cracking; if the concentrations are too low, the bottles are also attacked and the cleaning result is insufficient. In the ClP process is the last process often a disinfection step. In particular, contamination of foods with the frequently toxic disinfectants must be avoided and the post-rinsing process should therefore be monitored particularly carefully.
Die bisher bekannten Verfahren zur Konzentrationsbestimmung weisen jedoch Nachteile auf. Als Oπ-line-Messmethode wird die Leitfähig¬ keitsmessung durchgeführt. Damit Leitwertschwankungen im Leitungs¬ wasser nicht zu Messfehlern führen, setzt die sichere Durchführung dieser Methode einen relativ hohen Leitwert der Wirkstofflösung von üblicherweise mindestens 3 bis 4 mS voraus, der lediglich von stark alkalischen oder stark sauren Lösungen erreicht wird. Das Fehlen geeigneter On-line-Messmethoden für weitgehend neutrale Wirkstoff¬ lösungen, z. B. Desinfektionsmittel auf der Basis von quarterπären Ammoniumverbindungen oder Biguaniden, erschwert deren Einsatz für die CIP-Reinigung in der Lebensmittelindustrie erheblich. Wird in Flaschenreinigungsmaschinen die Leitfähigkeit als Maß für die Wirk¬ stoffkonzentration herangezogen, so täuschen die erhaltenen Werte eine zu hohe Wirkstoffkoπzentration vor, da durch den Eintrag von Kohlendioxid und durch z. B. aus der Auflösung von Aluminiumfolie erhaltene Salze die Leitfähigkeit der Lauge allmählich ansteigt.However, the previously known methods for determining the concentration have disadvantages. The conductivity measurement is carried out as an π-line measurement method. In order that fluctuations in the conductance in tap water do not lead to measurement errors, the safe implementation of this method requires a relatively high conductance of the active ingredient solution of usually at least 3 to 4 mS, which is only achieved by strongly alkaline or strongly acidic solutions. The lack of suitable on-line measurement methods for largely neutral active ingredient solutions, e.g. B. disinfectants based on quarterπäre ammonium compounds or biguanides, makes their use for CIP cleaning in the food industry considerably more difficult. If the conductivity is used in bottle cleaning machines as a measure of the active substance concentration, the values obtained simulate an excessively high active substance concentration, since carbon dioxide and z. B. salts obtained from the dissolution of aluminum foil gradually increases the conductivity of the alkali.
Eine andere, praxisübliche Art der Dosierung von Wirkstoffkonzen- traten ist die Dosierung proportional zum Flaschendurchsatz. Dieser Methode liegt die Überlegung zugrunde, daß jede Flasche mit der Flaschenzelle eine konstante Menge an Reinigungslauge aus dem Bad ausschleppt. Je nach Versteinung der Flaschenzellen, Schaumverhalten der Lösung und Lenkung der Flüssigkeitsströme zwischen den ver¬ schiedenen Bädern industrieller Flascheπreinigungsmaschinen ändert sich diese Menge jedoch. Aus der betrieblichen Praxis ist es be¬ kannt, daß bei der Dosierung nach den genannten Methoden die tat¬ sächliche Reinigungsmittelkonzentration im Laufe weniger Tage von der Sollkonzentration um 50 h oder mehr abweichen kann. Liegen technische Defekte der Dosiervorrichtung vor, können diese erst nach der in Intervallen von 1 bis 5 Tagen durchgeführten aufwendigen ma¬ nuellen Konzentrationsbestimmung erkannt und behoben werden. In diesen Fällen treten in der betrieblichen Praxis Konzentrations¬ schwankungen bis um den Faktor 40 auf.Another common way of dosing active ingredient concentrates is dosing proportional to the bottle throughput. This method is based on the consideration that each bottle with the bottle cell carries a constant amount of cleaning solution out of the bath. However, this amount changes depending on the petrification of the bottle cells, the foam behavior of the solution and the control of the liquid flows between the various baths of industrial bottle cleaning machines. From operational practice it is known that the actual detergent concentration can vary from the target concentration by 50 hours or more in the course of a few days when dosing according to the methods mentioned. Lie technical defects of the dosing device, these can only be recognized and corrected after the elaborate manual concentration determination carried out at intervals of 1 to 5 days. In these cases, concentration fluctuations of up to a factor of 40 occur in operational practice.
Genauer als die Leitfähigkeitsmessung arbeiten andere Bestimmungs¬ methoden, mit denen der Gehalt an Wirkstoff auf chemisch¬ analytischem Weg bestimmt wird. Diese Verfahren sind jedoch zeitin¬ tensiv, nur manuell durchführbar und können die Konzentration nicht kontinuierlich erfassen. So kann bei Jod / Jodid enthaltenden Wirk¬ stoffen, deren Konzentration in der Wirkstofflösung durch eine Be- Stimmung des in der Lösung vorhandenen Jods vorgenommen werden. Da¬ bei wird mittels Aktivkohlefiltration das Netzmittel aus einer Probe der Wirkstofflösung entfernt. Die in der Lösung vorhandenen Jodioneπ werden oxidiert. Vorhandenes Eiweiß wird durch Zugabe von Kupfer¬ sulfat gebunden. Nach einer Extraktion des Jods in Chloroform oder Methylenchlorid wird der Jodgehalt photometrisch bestimmt. Über eine Eichkurve kann daraus die Wirkstoffkonzentration ermittelt werden. Neben den oben genannten Nachteilen ist diese Methode sehr zeitin¬ tensiv und mit einer hohen Störanfälligkeit behaftet. Nachteilig ist ferner der notwendige Einsatz von chlorhaltigen Lösungsmitteln.Other determination methods, with which the content of active substance is determined chemically and analytically, work more precisely than the conductivity measurement. However, these methods are time-consuming, can only be carried out manually and cannot continuously detect the concentration. In the case of active substances containing iodine / iodide, their concentration in the active substance solution can be determined by determining the iodine present in the solution. The wetting agent is removed from a sample of the active ingredient solution by means of activated carbon filtration. The Jodioneπ present in the solution are oxidized. Existing protein is bound by adding copper sulfate. After extracting the iodine in chloroform or methylene chloride, the iodine content is determined photometrically. The active substance concentration can be determined from this using a calibration curve. In addition to the disadvantages mentioned above, this method is very time-consuming and has a high susceptibility to faults. Another disadvantage is the need to use chlorine-containing solvents.
Eine besondere Problematik liegt in dem Gehalt der Wirkstofflösung an Verunreinigungen, die zu Verfälschungen der Meßwerte führen können. Daher ist eine Vielzahl von denkbaren Verfahren zur Bestimmung der Konzentration in der Praxis nicht mit ausreichender Zuverlässigkeit einsetzbar.A particular problem lies in the content of impurities in the active ingredient solution, which can lead to falsifications of the measured values. Therefore, a large number of conceivable methods for determining the concentration cannot be used with sufficient reliability in practice.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art bereitzustellen, das zuverlässig, genau, schnell, wenig störanfällig und kontinuierlich arbeitet. Es soll ferner eine Automatisierung der Nachdosierung des Wirkstoffes ermöglichen. Insbesondere soll das erfindungsgemäße Verfahren in einer integrierten Reinigungstechnik, genannt "cleaning in place", einsetzbar sein. Es handelt sich dabei um große, zusammenhängende, voll automatische Reinigungssysteme, die alle Lagertank- und Lei¬ tungssysteme nach jedem Produktionsvorgang automatisch reinigen. Die Reinigungsprozeße werden von Kleinrechnern überwacht, so daß ein vorgegebener optimaler Hygieπestandard immer wieder aufs neue her¬ gestellt wird. Anwendung findet diese Technik in der Milchwirt¬ schaft, der Brauwirtschaft und der Getränkeindustrie.The invention is therefore based on the object of providing a method of the type mentioned at the outset which operates reliably, precisely, quickly, less susceptibly to faults and continuously. It is also intended to automate the replenishment of the active ingredient enable. In particular, the method according to the invention should be able to be used in an integrated cleaning technique called "cleaning in place". These are large, coherent, fully automatic cleaning systems which automatically clean all storage tank and line systems after each production process. The cleaning processes are monitored by small computers, so that a predetermined optimal hygiene standard is produced again and again. This technology is used in the dairy, brewing and beverage industries.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man die Jod¬ ionenkonzentration in der Lösung potentiometriseh mittels auf Jodionen selektiv ansprechender Elektroden mißt und aus den erha.- tenen Meßwerten die Konzentration des Wirkstoffs bestimmt, wobei die Jod/Jodid-Konzentration in der Lösung zwischen 0,1 und 1000 ppm liegt. Insbesondere liegt die Jod/Jodid-Kozentration in der Lösung im Bereich zwischen 1 und 20 ppm.This object is achieved according to the invention in that the iodine ion concentration in the solution is measured potentiometrically by means of electrodes which selectively respond to iodine ions and the concentration of the active substance is determined from the measured values obtained, the iodine / iodide concentration in the solution being between 0 , 1 and 1000 ppm. In particular, the iodine / iodide concentration in the solution is in the range between 1 and 20 ppm.
Vorteilhaft wird das erfindungsgemäße Verfahren zur Messung der Wirkstoffkonzentration in den Laugenbädern und Wasserzonen in¬ dustrieller Flaschenreinigungsmaschinen eingesetzt.The method according to the invention is advantageously used to measure the concentration of active substance in the caustic baths and water zones of industrial bottle cleaning machines.
Bevorzugt ist ebenfalls, daß das Verfahren zur Messung der Wirk¬ stoffkonzentration von Reinigungs- oder Desinfektionsmittellösungen für ClP-Prozesse in der Lebensmittelindustrie eingesetzt wird.It is also preferred that the method for measuring the active substance concentration of cleaning or disinfectant solutions is used for ClP processes in the food industry.
In einer weiteren vorteilhaften Ausführungsform wird das Verfahren zur Messung der Wirkstoffkonzentration in industriellen Durchlauf¬ waschanlagen insbesondere für die Reinigung von Blechen oder Textilien eingesetzt, wobei insbesondere die zu reinigenden, durchlaufenden Gegenstände einen Teil der Wirkstofflösung aus den Wirkstoffbädern ausschleppen. Bevorzugt bestimmt man die Konzentration des Wirkstoffs aus dem ge¬ messenen Potential mittels einer Eichkurve, die durch die gemessenen Potentiale mindestens zweier unterschiedlicher Konzentrationen des Wirkstoffs in der zu überwachenden Lösung festgelegt worden ist. Man erhält besonders zuverlässige Meßwerte, da man die in der Praxis vorliegende Lösung mit den typischen Verunreinigungen des speziellen Reinigungs- und Desinfektionsvorgangs zur Eichung heranzieht. Es hat sich dabei als vorteilhaft herausgestellt, wenn die zur Eichung verwendeten Meßpunkte einen Konzentrationsbereich zwischen einer und zwei Dekaden umfassen.In a further advantageous embodiment, the method for measuring the active substance concentration in industrial continuous washing systems is used in particular for the cleaning of metal sheets or textiles, the objects to be cleaned, in particular, being dragged out of the active substance baths by part of the active substance solution. The concentration of the active ingredient is preferably determined from the measured potential by means of a calibration curve which has been determined by the measured potentials of at least two different concentrations of the active ingredient in the solution to be monitored. Particularly reliable measured values are obtained since the solution present in practice with the typical impurities of the special cleaning and disinfection process is used for calibration. It has turned out to be advantageous if the measuring points used for the calibration comprise a concentration range between one and two decades.
Insbesondere ist die direkte Potentiometrie bei der Ausübung des erfiπdungsge äßen Verfahrens vorteilhaft, da sie ohne größeren Auf¬ wand sofort aktuelle Meßwerte liefert. Ein Einbau in eine automa¬ tische Dosiervorrichtung ist außerdem problemlos. Bei der Eichung ist es zweckmäßig, die erhaltenen Potentiale gegen den Logarithmus der Konzentrationen aufzutragen, so daß eine Eichgerade erhalten wird.In particular, direct potentiometry is advantageous when carrying out the method according to the invention, since it immediately delivers current measured values without great expense. Installation in an automatic metering device is also problem-free. During the calibration, it is expedient to plot the potentials obtained against the logarithm of the concentrations, so that a calibration line is obtained.
Ein weiterer Aspekt der Erfindung betrifft das Dosieren/Nachdosieren eines Jod/Jodid enthaltenden Wirkstoffs in eine wäßrige Wirkstoff¬ lösung. Dabei wird erfindungsgemäß die Dosierung von einer Regel¬ einrichtung gesteuert, die die erfiπdungsgemäß ermittelte Ist¬ konzentration mit einer vorgegebenen Sollkonzeπtration vergleicht. Mit diesem Dosierverfahren läßt sich eine integrierte Reinigungs¬ technik ("cleaning in place") aufbauen.Another aspect of the invention relates to the dosing / re-dosing of an active substance containing iodine / iodide into an aqueous active substance solution. According to the invention, the metering is controlled by a control device which compares the actual concentration determined according to the invention with a predetermined target concentration. An integrated cleaning technology ("cleaning in place") can be built up with this dosing method.
In einer weiteren bevorzugten Ausführungsform der Erfindung trennt man Vor- oder Nachspülwässer in ClP-Prozessen von der wäßrigen Wirkstofflösung (Phasentrennung), indem die Phasentrennuπg von einer Einrichtung gesteuert wird, die die ermittelte Konzentration des Wirkstoffs mit einer vorgegebenen Sollkonzentration vergleicht und entsprechend dem Vergleichsergebnis Ventile zur Phasentrennung an¬ steuert.In a further preferred embodiment of the invention, pre-rinse or rinse water is separated from the aqueous active substance solution (phase separation) in ClP processes by controlling the phase separation by a device which compares the determined concentration of the active substance with a predetermined target concentration and controls valves for phase separation in accordance with the comparison result.
Im folgenden werden Versuchsergebnisse mit dem erfindungsgemäßen Verfahren näher beschrieben.Test results using the method according to the invention are described in more detail below.
An einer Flaschwaschmaschine für wiederbefüllbare PET-Flaschen wur¬ den Konzeπtrations essungen mit selektiv auf Jodionen ansprechenden Elektroden durchgeführt. Um die Zuverlässigkeit der neuen Methode zu überprüfen, wurde die Reinigungsmittelkonzentration zum Vergleich auch photometrisch, wie es oben beschrieben ist, bestimmt.Concentration measurements with electrodes selectively responding to iodine ions were carried out on a bottle washing machine for refillable PET bottles. To check the reliability of the new method, the detergent concentration was also determined photometrically for comparison, as described above.
In einem Durchflußbecher wurden eine Jodidelektrode und eine ge¬ wöhnliche pH-Elektrode als Gegenelektrode installiert. Durch den Becher wurde die Reinigungslauge aus einer laufenden Flaschenwasch¬ maschine geleitet. Die verstärkten Meßsignale registrierte man auf einem Schreiber. Zunächst wurde eine Eichkurve aufgenommen, in der das Potential der Originallauge und der Lauge nach einer Erhöhung der Reinigungsmittelkonzentration um den Faktor 10 gemessen wurde. Die Konzentration des Reinigungsmittels in der Originallauge wurde photometrisch bestimmt. Die Eichgerade wurde erstellt, indem der Logarithmus der Potentiale gegen die Konzentration aufgetragen wur¬ de. Um die Korrelation der potentiometrisch bestimmten Konzentrati¬ onswerte mit den aus der photometrischen Bestimmung ermittelten über einen weiten Bereich zu erfassen, wurde portionsweise während der Messung Reinigungsmittel zudosiert. Bei dem Reinigungsmittel handelt es sich um das Handelsprodukt P3-Stabi1on AL flüssig, einem Wirk¬ stoffkonzentrat für die Flaschenreinigung, das auch zur Entfernung von Aluminiumfolien, -etiketten und -kapseln geeignet ist. Die er¬ haltenen Ergebnisse finden sich für eine Reinigungslauge mit Ver¬ schmutzungen in Tabelle 1 und für eine frische Reinigungslauge in Tabelle 2. Die Zuverlässigkeit und Genauigkeit des erfindungsgemäßen Verfahrens und damit dessen hervorragende Eignung für einen Einsatz in der Praxis sind daraus ersichtlich.An iodide electrode and a common pH electrode were installed as the counter electrode in a flow cup. The cleaning liquor was passed through the cup from a running bottle washing machine. The amplified measurement signals were registered on a recorder. First, a calibration curve was recorded, in which the potential of the original solution and the solution was measured after increasing the detergent concentration by a factor of 10. The concentration of the detergent in the original solution was determined photometrically. The calibration line was created by plotting the logarithm of the potentials against the concentration. In order to determine the correlation of the potentiometrically determined concentration values with those determined from the photometric determination over a wide range, detergents were added in portions during the measurement. The cleaning agent is the commercial product P3-Stabi1on AL liquid, an active ingredient concentrate for bottle cleaning, which is also suitable for removing aluminum foils, labels and capsules. The results obtained are found in Table 1 for a cleaning solution with soiling and in Table 2 for a fresh cleaning solution. The reliability and accuracy of the invention Process and thus its excellent suitability for use in practice can be seen from this.
Tabelle 1: Gehalt an P3-Stabilon in % in verschmutzter LaugeTable 1: P3-Stabilon content in% in soiled lye
Tabelle 2: Gehalt an P3-Stabilon in % in frischer LaugeTable 2: P3 stabilone content in% in fresh alkali

Claims

P a t en t a n s p rü c h eP a t en t a n s rü c h e
1. Verfahren zum Bestimmen der Konzentration eines Jod/Jodid enthaltenden Wirkstoffs in wäßrigen Wirkstofflösungen, die insbesondere zur Reinigung oder Desinfektion von Behältern wie Flaschen, Fässern, Kegs, Kästen und Tanks und/oder Rohrleitungen in der lebens ittelverarbeitenden Industrie sowie zur industriellen Reinigung in DurchlaufWaschanlagen eingesetzt werden, wobei die Konzentration der Wirkstoffe in der Lösung über eine Bestimmung ihres Jod/Jodid-Gehalts gemessen wird, d a d u r c h g e k e n n z e i c h n e t, daß man die Jodionenkonzentration in der Lösung potentiometrisch mittels auf Jodionen selektiv ansprechender Elektroden mißt und aus den erhaltenen Meßwerten die Konzentration des Wirkstoffes bestimmt, wobei die Jod/Jodid-Konzentration in der Lösung zwischen 0,1 und 1000 ppm liegt.1. A method for determining the concentration of an active ingredient containing iodine / iodide in aqueous active ingredient solutions, in particular for cleaning or disinfecting containers such as bottles, barrels, kegs, boxes and tanks and / or pipelines in the food processing industry and for industrial cleaning in continuous washing systems are used, the concentration of the active substances in the solution being measured by determining their iodine / iodide content, characterized in that the iodine ion concentration in the solution is measured potentiometrically by means of electrodes which selectively respond to iodine ions and the concentration of the active substance is determined from the measured values obtained , the iodine / iodide concentration in the solution being between 0.1 and 1000 ppm.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, daß die Jod/Jodid-Konzentration in der Lösung zwischen 1 und 20 ppm liegt.2. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that the iodine / iodide concentration in the solution is between 1 and 20 ppm.
3. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, daß das Verfahren zur Messung der Wirkstoffkonzentration in den Laugenbädern und Wasserzonen industrieller Flaschenreinigungs maschinen eingesetzt wird.3. The method according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that the method for measuring the concentration of active ingredient in the caustic baths and water zones of industrial bottle cleaning machines is used.
4. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, daß das Verfahren zur Messung der Wirkstoffkonzentration von Reinigungs- oder Desinfektionsmittellösungen für ClP-Prozesse in der Lebensmittelindustrie eingesetzt wird. 5. Verfahren nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t, daß das Verfahren zur Messung der Wirkstoffkonzentration in industriellen DurchlaufWaschanlagen, insbesondere für die Reinigung von Biechen oder Textilien eingesetzt wird, wobei die zu reinigenden, durchlaufenden Gegenstände einen Teil der Wirkstofflösung aus den Wirkstoffbädern ausschleppen.4. The method according to claim 1 or 2, characterized in that the method for measuring the active ingredient concentration of cleaning or disinfectant solutions for ClP processes in the food industry is used. 5. The method according to any one of claims 1 to 3, characterized in that the method for measuring the active ingredient concentration in industrial continuous washing systems, in particular for the cleaning of beeches or textiles is used, the objects to be cleaned, continuous objects carry out part of the active ingredient solution from the active ingredient baths .
5. Verfahren nach einem der Ansprüche 1 bis 5, d a d u r c h g e k e n n z e i c h n e t, daß man die Konzentration des Wirkstoffs aus dem gemessenen Po¬ tential mittel einer Eichkurve bestimmt, die durch die gemes- senen Potentiale mindestens zweier unterschiedlicher Konzentra¬ tionen des Wirkstoffs in der zu überwachenden Lösung festgelegt worden ist.5. The method according to any one of claims 1 to 5, characterized in that the concentration of the active ingredient is determined from the measured potential by means of a calibration curve, which is measured by the measured potentials of at least two different concentrations of the active ingredient in the solution to be monitored has been established.
7. Verfahren nach Anspruch 6, d a d u r c h g e k e n n z e i c h n e t, daß die zur Eichung verwendeteten Meßpuπkte einen Koπzentratioπsbereich zwischen einer und zwei Dekaden umfassen.7. The method of claim 6, d a d u r c h g e k e n n z e i c h n e t that the measurement points used for calibration comprise a concentration range between one and two decades.
8. Verfahren nach einem der Ansprüche 1 bis 7, d a d u r c h g e k e n n z e i c h n e t, daß die direkte Potentiometrie angewendet wird.8. The method according to any one of claims 1 to 7, d a d u r c h g e k e n n z e i c h n e t that the direct potentiometry is used.
9. Verfahren nach einem der Ansprüche 1 bis 8, d a d u r c h g e k e n n z e i c h n e t, daß man den Jod/Jodid enthaltenden Wirkstoff in eine wäßrige Wirkstofflösung dosiert/nachdosiert, wobei die Dosierung von einer Regeleinrichtung gesteuert wird, die die ermittelte Ist- Konzentration mit einer vorgegebenen Sollkonzentration ver¬ gleicht. 10. Verfahren nach einem der Ansprüche 1 bis 8, d a d u r c h g e k e n n z e i c h n e t, daß man Vor- oder Nachspülwässer in ClP-Prozessen von der wäßrigen Wirkstofflösung trennt (Phasentrennung), indem die Phasentrennung von einer Einrichtung gesteuert wird, die die ermittelte Konzentration des Wirkstoffs mit einer vorgegebenen Sollkonzentratioπ vergleicht und entsprechend dem Vergleichser¬ gebnis Ventile zur Phasentrennung ansteuert. 9. The method according to any one of claims 1 to 8, characterized in that the active substance containing iodine / iodide is metered / replenished in an aqueous active substance solution, the metering being controlled by a control device which ver¬ the determined actual concentration with a predetermined target concentration equal. 10. The method according to any one of claims 1 to 8, characterized in that pre-rinse or rinse water in ClP processes from the aqueous active ingredient solution is separated (phase separation) by the phase separation is controlled by a device that determines the concentration of the active ingredient with a predetermined Comparing the target concentration and controlling valves for phase separation in accordance with the comparison result.
EP92917156A 1991-08-22 1992-08-13 Method of determining and controlling the concentration of active substances included for cleaning and disinfection purposes in aqueous cleaning and disinfection-agent solutions Ceased EP0599907A1 (en)

Applications Claiming Priority (3)

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DE4127663A DE4127663A1 (en) 1991-08-22 1991-08-22 METHOD FOR DETERMINING AND REGULATING THE CONCENTRATION OF ACTIVE SUBSTANCES FOR CLEANING AND DISINFECTION IN WAESSED CLEANSING AND DISINFECTANT SOLUTIONS
DE4127663 1991-08-22
PCT/EP1992/001846 WO1993004361A1 (en) 1991-08-22 1992-08-13 Method of determining and controlling the concentration of active substances included for cleaning and disinfection purposes in aqueous cleaning and disinfection-agent solutions

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DE19814500A1 (en) * 1998-04-01 1999-10-14 Henkel Kgaa Automatic control and regulation of the surfactant content in aqueous process solutions
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DE19959311A1 (en) * 1999-12-09 2001-08-23 Henkel Ecolab Gmbh & Co Ohg Defoamer preparation and its use
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