EP3122863B1 - Procédé pour le nettoyage d'installations - Google Patents

Procédé pour le nettoyage d'installations Download PDF

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Publication number
EP3122863B1
EP3122863B1 EP15726856.6A EP15726856A EP3122863B1 EP 3122863 B1 EP3122863 B1 EP 3122863B1 EP 15726856 A EP15726856 A EP 15726856A EP 3122863 B1 EP3122863 B1 EP 3122863B1
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EP
European Patent Office
Prior art keywords
value
color
composition
cleaning
determined
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Application number
EP15726856.6A
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German (de)
English (en)
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EP3122863A1 (fr
Inventor
Daniel Herzog
Philip Thonhauser
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Thonhauser GmbH
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Thonhauser GmbH
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Priority to SI201530271T priority Critical patent/SI3122863T1/en
Priority to RS20180599A priority patent/RS57251B1/sr
Priority to PL15726856T priority patent/PL3122863T3/pl
Priority to HRP20180895TT priority patent/HRP20180895T1/hr
Publication of EP3122863A1 publication Critical patent/EP3122863A1/fr
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Publication of EP3122863B1 publication Critical patent/EP3122863B1/fr
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    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • 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
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67D—DISPENSING, DELIVERING OR TRANSFERRING LIQUIDS, NOT OTHERWISE PROVIDED FOR
    • B67D1/00—Apparatus or devices for dispensing beverages on draught
    • B67D1/07—Cleaning beverage-dispensing apparatus
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • 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
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to a method for cleaning plants while simultaneously detecting the purity of the plant.
  • EP 1,343,864 A1 and EP 1,730,258 A1 (equivalent to WO 2005/044968 A1 ) also discloses the Applicant water-soluble, permanganate-containing detergents and disinfectants, which in addition to permanganate a second oxidizing agent is used, which sometimes serves as the main oxidizing agent, while the permanganate predominantly indicator function plays.
  • the base color value of the cleaning composition herein simultaneously referred to as F B prior to entering the system to be cleaned, does not serve as a benchmark for determining the purity of the system. Rather, according to the present invention, so to speak for the "calibration" of the process, the system is first flushed through to the surface until a constant color value is obtained.
  • the constancy of the plant-specific color value named F A indicates that no more oxidisable impurities are contained in the plant.
  • this "self-degradation" is temperature dependent and, moreover, is still strongly dependent on the size of the plant, i. of its inner surface and the residence time therein, as well as of course depends on the accuracy in the preparation of the composition.
  • the value for F A can be determined several times using different water temperatures, as they are within the natural fluctuation range-during the corresponding season or over the entire calendar year-in order to bring out the influence of temperature.
  • inaccuracies in mixing the usually commercially available concentrates for the cleaning composition can be averaged out by the sample weighed in steps of 1% ⁇ 5 wt .-% is varied and the respective color values are determined and used for averaging.
  • these are preferably carried out in each case in the course of cleaning operations after interim operation of the system.
  • the color value of the exiting composition can be measured to constancy, so that over time an ever more accurate average for F A is obtained, are taken into account in the temperature, air and concentration fluctuations or influences.
  • a base color value F B of the composition without passage of the plant can be determined Value for F A , so as to obtain an increasingly accurate general correlation between F B and F A over time in an iterating manner.
  • this value for F B does not serve, as in the prior art, as a reference point for the determination of the desired value, but merely represents an alternative or preferably Also in addition to the multiple determinations described above. Rather than over time to obtain an increasingly accurate average for F A , in which temperature and other factors are taken into account, according to this preferred embodiment of the invention, the "Ausstoffn" these influences ad hoc respectively. After repeated, in particular frequent, implementation of steps a) to e) and the resulting receipt of a reliable correlation between F B and F A , only the basic color value F B needs to be determined for a particular installation in step c), while the inherent investment value F A of the correlation between F and B F A can be calculated. This therefore simplifies and accelerates the process of the invention significantly and at the same time ensures high accuracy in the determination of purity.
  • the target value ⁇ F A which is determined based on the inherent plant value F A determined initially at the "calibration" of the plant and serves as a reference for the measurement during the following cleaning operations, is not particularly limited and may vary depending on several factors. These include above all the intended use of the plant itself, for example, whether this is for drinks or other food or not for food, the frequency of cleaning, the costs necessary to achieve a certain purity and the time required for it, but also the reliability of the inherent Asset value F A. The latter depends above all on whether the value is based on multiple determinations, if so, on their number and on which influences were taken into account in the mean value (eg temperature, water quality, etc.).
  • the last difference .DELTA.F can be given greater zero before reaching the values constant as the desired value .DELTA.F A, or a certain percentage deviation from the inherent investment value F A, for example 95% thereof, or the like. Since the method according to the invention primarily results in a saving of cleaning composition, a relatively large deviation of F A can sometimes be specified as the setpoint, as long as this is possible, for example, without infringing relevant hygiene regulations.
  • a digital camera is preferably used in accordance with the present invention, and a color comparison software, for example for calculating the difference values .DELTA.F, is used.
  • software capable of converting RBG values recorded by the camera (unless the camera directly captures RGB values) and comparing these RGB values, e.g. by a vector subtraction method, wherein the magnitude of the difference vector is the respective difference ⁇ F.
  • the colorant-containing cleaning composition in preferred embodiments comprises permanganate as a color indicator and at least one further oxidizing agent whose oxidation potential is above that of permanganate as described above, more preferably peroxodisulfate, hypochlorite or a mixture thereof, v. due to the high sensitivity and strong oxidation effect of such systems.
  • permanganate as a color indicator
  • at least one further oxidizing agent whose oxidation potential is above that of permanganate as described above, more preferably peroxodisulfate, hypochlorite or a mixture thereof, v. due to the high sensitivity and strong oxidation effect of such systems.
  • oxidizing agent e.g. e.g. Potassium iodide, dichromate or dichlorophenolindophenol in combination with hydrogen peroxide or ferroin for persulfate.
  • color value is not necessarily an RGB value.
  • the principle of the invention works with all physical data that allow conclusions to be drawn on the concentration of manganese ion species in the cleaning composition leaving the unit - and consequently on the amount of impurities oxidized in the just-done passage of the unit. These include, for example, photometrically measured extinction values, the refractive index or else the pH of the cleaning composition emerging from the plant.
  • the principle of the invention works not only with difference values, but also with other relations between two temporally successive color value measurements. Instead of differences, it is also possible, for example, to form quotients of the two last measured values obtained, in which case consistency of the cleaning composition not at a difference value of 0, but at a quotient of 1 vorläge.
  • the setpoint may be a percentage deviation thereof, eg, a value of 0.95 or 1.05, depending on whether the color value increases or decreases as it approaches the constant inherent plant value F A. See also the explanations in the later examples, especially in connection with the Fig. 5 and 6 ,
  • FIG. 1 to 4 schematic representations of three different embodiments of the method of the invention
  • Fig. 5 and 6 are graphical representations of color values measured in one embodiment of the method according to the invention.
  • FIG. 1 A simplest embodiment of the method according to the invention is in Fig. 1 shown.
  • a reservoir 1 for the cleaning composition it is continuously passed through a system 2 to be cleaned, whereafter it passes through a sensor 3 in which color values and their differences are determined at regular intervals.
  • the length of the time interval depends significantly on the size of the system and the associated residence time of the composition in the system - from entry to re-exit - from.
  • the residence time may be around 15 minutes, in which case the color value may be determined, for example, every 2 minutes or every 5 minutes.
  • a maximum allowable deviation ⁇ F A is defined, which can be reached at the next cleaning of the system after its operation in order to be able to treat the system as sufficiently pure.
  • the size of this setpoint depends on various considerations and circumstances. For example, the last measured difference> 0 can be used as the desired value ⁇ F A. This would mean that, according to the method of the invention, flushing of the equipment could be stopped a few minutes earlier, saving material costs (for the cleaning composition), energy and time.
  • a greater difference than ⁇ F A is set to increase the savings potential, eg, a difference between F A and that measured before the complete last run of the equipment, ie, 15, for example measured before reaching the zero difference value, or, as already mentioned, a percentage deviation of F A.
  • the reliability of the inherent plant value F A it is preferably determined several times: be it several times on the same day, eg with different temperatures of the water used to prepare the cleaning composition and / or slightly varying concentrations of the cleaning composition, or on different days, in addition to the parameters mentioned also the influences of the ambient air to include.
  • the value for F A is first determined for each cleaning of the system over a certain period of time.
  • F A becomes an average value obtained in which several variables have been taken into account, so you can always be sure to have the plant actually sufficiently cleaned during demolition of the cleaning process by measuring a color value difference ⁇ .DELTA.F A.
  • the length of this "certain period" depends on the frequency of cleaning and various other conditions. For example, in a weekly cleaning, the F A value may be determined for several months or even a whole year to obtain a representative mean.
  • the self-degradation of the cleaning composition in the plant is taken into account in the assessment of plant purity, which has hitherto never been the case in the prior art.
  • Fig. 2 shows a preferred embodiment of the method Fig. 1 in which, parallel to the line through the plant 2, a bypass line B is provided, through which the cleaning composition - by means of actuation of the in the drawing by reference numerals 4 and 4 'indicated three-way valves can be passed without first to pass the plant itself.
  • F B a so-called basic color value
  • F B according to the present invention is not measured by its own sensor before it enters the system but by the same sensor 3 downstream of the system as in the course of the actual cleaning.
  • F B does not serve as a set point in the cleaning, but only for more accurate determination of the inherent plant value F A or the difference ⁇ F A based thereon.
  • the base color value F B measured in this way can furthermore be compared with F A , preferably with a value for F A measured in each case on the same day, so as to obtain a more and more precise correlation between F B and F A over time, for example a can be defined calculation formula or a calibration curve derived therefrom.
  • a corresponding value for F A can be estimated from a measured value for F B from the correlation obtained with high precision, without having to determine this separately. Namely a value for F A , in which daily fluctuations (see above) are already taken into account.
  • Fig. 3 a variant of the method according to the invention is shown schematically, in which in contrast to the embodiment of the Fig. 1 and 2 the composition leaving the unit is not completely removed (and sometimes discarded), but is at least partially recycled and blended with fresh detergent composition.
  • a three-way valve is indicated, by means of which the ratio between recycled and to be discarded cleaning composition is adjustable.
  • Fig. 4 is a similar variant as in Fig. 2 shown with bypass, in addition to the arrangement of Fig. 3 in a bypass circuit B between the valves 4 and 4 ', the basic color value FB of the cleaning composition at sensor 3 can be measured and in turn correlated with the inherent plant value F A. After determining the basic color value F B , the bypass B is switched off, so that the cleaning composition as in Fig. 3 shown is performed. By means of valve 4 "is again the ratio between recycled and discarded cleaning composition adjustable.
  • an additional sensor 3 ' may be provided which is similar to DE 10 2006 060 204 A1 measures another base color value F B ' before entering the system. This value can also be correlated with either F A or F B, or both, to further increase the accuracy of the calibration.
  • the method of the invention works well even without such a second sensor.
  • Fig. 5 shows the results of the measurements at both temperatures as well as at 535 nm wavelength, ie the change in violet coloration due to permanganate, which is a measure of the presence of manganese (VII) in the composition.
  • a similar course was observed at both temperatures: after addition of the impurity, the content of manganese (VII) dropped abruptly from the inherent plant value F A applied as starting point, which in this case was at an extinction of about 0.1. but recovered quickly - due to the small dimensions of the test system after a few seconds - again and then slowly approached the initial value F A again.
  • a differential value .DELTA.F drawn ie .DELTA.F RT or .DELTA.F 40 ° C , each of which corresponds to about 5% of the original extinction, ie of F A , and which can be used as setpoint .DELTA.F A for the system used here.
  • the impurities remaining in hard-to-reach places would consist of components of a normal operation of the plant, which as such could not disturb the process itself (at least as long as it is not perishable food), especially since (ii) these residual impurities are generally contained only in extremely small amounts but are sufficient to initiate the self-degradation of the permanganate.
  • ⁇ F A can have a positive or negative value depending on the type of color value measured.
  • the decisive factor is therefore only the amount of this difference, ie the extent of Farbwerts- and thus the concentration change of the cleaning composition, but not the sign.
  • the invention thus obviously provides a new process by which plants, such as e.g. Dispensing or bottling plants can be cleaned in a significantly more economical manner than in the prior art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Cleaning In General (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Detergent Compositions (AREA)

Claims (8)

  1. Procédé pour nettoyer un système, comprenant le passage d'une composition de nettoyage comprenant au moins un agent oxydant pour oxyder des contaminations, ainsi que le passage d'une composition indicatrice pour détecter l'état de propreté du système moyennant l'observation d'un changement de couleur de la composition indicatrice, l'observation consistant à déterminer des valeurs chromatiques de la composition indicatrice à un ou plusieurs positions, mais au moins après sa sortie du système, et à les comparer avec une valeur désirée;
    a) une composition de nettoyage contenant un indicateur de couleur, qui en même temps sert de composition indicatrice, étant employée; et
    b) la composition étant passée dans le système de manière continue;
    caractérisé en ce que:
    c) les valeurs chromatiques F de la composition sont déterminées, après la sortie de celle-ci du système, dans des intervalles de temps prédéfinies;
    d) des différences ΔF obtenues à partir de deux déterminations successives sont formées;
    e) avant le démarrage du système propre les valeurs sont déterminés jusqu'à ce qu'une différence ΔF de 0 soit déterminée, après quoi la valeur chromatique mesurée en dernier est définie comme valeur intrinsèque du système FA et une déviation tolérée maximale de cette valeur est définie comme valeur désirée ΔFA pour le nettoyage; et
    f) le nettoyage du système est effectué après le démarrage de ce dernier jusqu'à ce que la différence ΔFR entre deux valeurs chromatiques successives FR soit égale ou inférieure à ΔFA, ce qui indique la propreté du système.
  2. Procédé selon la revendication 1, caractérisé en ce que la valeur intrinsèque du système FA est mesurée plusieurs fois dans l'étape c)
    - à de températures différentes de la composition et/ou
    - avec des concentrations indicatrices différentes et/ou
    - dans des journées différentes
    et une valeur moyenne est formée, qui est utilisée comme valeur intrinsèque du système FA à partir de laquelle est calculée la valeur désirée ΔFA.
  3. Procédé selon la revendication 2, caractérisé en ce que les déterminations multiples de FA sont à chaque fois effectuées lors des opérations de nettoyage, après le fonctionnement intermédiaire du système.
  4. Procédé selon les revendications 2 ou 3, caractérisé en ce que dans l'étape c), lors de chaque détermination multiple de la valeur intrinsèque du système FA, est déterminée, sous les mêmes conditions de température et/ou de concentration, également une valeur chromatique de base FB de la composition sans passage dans le système à nettoyer, qui est corrélée avec la valeur FA obtenue, pour obtenir par itération une corrélation générale entre FB et FA.
  5. Procédé selon la revendication 4, caractérisé en ce qu'après effectuation multiple des étapes a) à e), lors de l'étape c) est déterminée uniquement la valeur chromatique de base FB et calculée la valeur intrinsèque du système FA à partir de la corrélation entre FB et FA.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que pour déterminer les valeurs chromatiques est employée une caméra numérique et pour calculer les différences ΔF est employé un logiciel de comparaison de couleur.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la composition de nettoyage contenant un indicateur de couleur comprend du permanganate comme indicateur de couleur ainsi qu'au moins un autre agent oxydant, dont le potentiel d'oxydation est supérieur à celui du permanganate.
  8. Procédé selon la revendication 7, caractérisé en ce que comme autre agent oxydant est employé du peroxodisulfate, de l'hypochlorite ou un mélange de ceux-ci.
EP15726856.6A 2014-03-26 2015-03-24 Procédé pour le nettoyage d'installations Active EP3122863B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
SI201530271T SI3122863T1 (en) 2014-03-26 2015-03-24 Procedure for cleaning plants
RS20180599A RS57251B1 (sr) 2014-03-26 2015-03-24 Postupak za čišćenje sistema
PL15726856T PL3122863T3 (pl) 2014-03-26 2015-03-24 Sposób czyszczenia urządzeń
HRP20180895TT HRP20180895T1 (hr) 2014-03-26 2015-03-24 Postupak za čišćenje sustava

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA217/2014A AT515571B1 (de) 2014-03-26 2014-03-26 Verfahren zum Reinigen von Anlagen
PCT/AT2015/050073 WO2015143468A1 (fr) 2014-03-26 2015-03-24 Procédé pour le nettoyage d'installations

Publications (2)

Publication Number Publication Date
EP3122863A1 EP3122863A1 (fr) 2017-02-01
EP3122863B1 true EP3122863B1 (fr) 2018-03-14

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EP15726856.6A Active EP3122863B1 (fr) 2014-03-26 2015-03-24 Procédé pour le nettoyage d'installations

Country Status (14)

Country Link
US (1) US10190080B2 (fr)
EP (1) EP3122863B1 (fr)
CN (1) CN106459848B (fr)
AT (1) AT515571B1 (fr)
DK (1) DK3122863T3 (fr)
ES (1) ES2671477T3 (fr)
HR (1) HRP20180895T1 (fr)
HU (1) HUE038035T2 (fr)
PL (1) PL3122863T3 (fr)
PT (1) PT3122863T (fr)
RS (1) RS57251B1 (fr)
SI (1) SI3122863T1 (fr)
TR (1) TR201807247T4 (fr)
WO (1) WO2015143468A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102019100961A1 (de) 2019-01-15 2020-07-16 Ossberger Gmbh + Co Kg Bewertungsverfahren für einen Reinigungszustand eines Werkstücks sowie eine Vorrichtung zur Durchführung des Verfahrens

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DK3122863T3 (en) 2018-06-14
PL3122863T3 (pl) 2018-08-31
US20170191006A1 (en) 2017-07-06
CN106459848B (zh) 2020-04-17
AT515571A1 (de) 2015-10-15
CN106459848A (zh) 2017-02-22
AT515571B1 (de) 2018-01-15
PT3122863T (pt) 2018-05-29
WO2015143468A1 (fr) 2015-10-01
EP3122863A1 (fr) 2017-02-01
ES2671477T3 (es) 2018-06-06
TR201807247T4 (tr) 2018-06-21
HUE038035T2 (hu) 2018-09-28
HRP20180895T1 (hr) 2018-07-13
RS57251B1 (sr) 2018-08-31
US10190080B2 (en) 2019-01-29
SI3122863T1 (en) 2018-07-31

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