EP3337916B1 - Solution de nettoyage aqueuse destinée à éliminer rouging sur des surfaces en contact avec le fluide d'aciers inoxydables, son utilisation et son procédé de fabrication - Google Patents

Solution de nettoyage aqueuse destinée à éliminer rouging sur des surfaces en contact avec le fluide d'aciers inoxydables, son utilisation et son procédé de fabrication Download PDF

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Publication number
EP3337916B1
EP3337916B1 EP16769870.3A EP16769870A EP3337916B1 EP 3337916 B1 EP3337916 B1 EP 3337916B1 EP 16769870 A EP16769870 A EP 16769870A EP 3337916 B1 EP3337916 B1 EP 3337916B1
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EP
European Patent Office
Prior art keywords
cleaning solution
sulfite
aqueous
alkali
formate
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.)
Active
Application number
EP16769870.3A
Other languages
German (de)
English (en)
Other versions
EP3337916A1 (fr
Inventor
Alexander Pohl
Gunter Rolf BLUMHOFER
Michael Hugo GÖBEL
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.)
Beratherm AG
Original Assignee
Beratherm AG
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 Beratherm AG filed Critical Beratherm AG
Priority to SI201630387T priority Critical patent/SI3337916T1/sl
Publication of EP3337916A1 publication Critical patent/EP3337916A1/fr
Application granted granted Critical
Publication of EP3337916B1 publication Critical patent/EP3337916B1/fr
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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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • C11D2111/16—Metals

Definitions

  • the present invention relates to an aqueous cleaning solution for removing Rougingbelägen on media-contacting surfaces of stainless steels according to the preamble of claim 1. Furthermore, the invention relates to a use of the inventive cleaning solution and a process for their preparation.
  • Rouging Numerous plants in the pharmaceutical, biotechnology and food industries include piping systems for pure or ultrapure water or pure steam, which are usually made of austenitic stainless steels. It is generally known that the media-touched inner surfaces of such mostly tempered systems after an operating time of several weeks to months develop a yellow, red to black violet, often reddish brown to rust-colored surface discoloration, which is referred to in the jargon as "rouging".
  • the main components of "rouging” are various iron oxides and iron hydroxides with iron in the oxidation state +3, which may contain fractions of chromium, nickel and molybdenum.
  • Rouging layers are detectable not only visually, but, for example, with a common Weisswischtuchtest and are more or less easily wiped depending on the severity. Rouging layers can lead to contamination of downstream systems by entrainment of the layer particles and are highly undesirable for this reason alone. Accordingly, the removal of Rougingbelägen, also called “derouging", an important aspect of the maintenance of the above-mentioned piping systems and the like. It is crucial that the Rougingbeläge in useful Deadline and as completely as possible, without the surface, such as the electropolishing, damaged.
  • the object of the present invention was therefore to provide an improved aqueous cleaning solution for removing Rougingbelägen on media-contacting surfaces of stainless steels. Further objects of the invention are the specification of a use or a method for producing the inventive cleaning solution.
  • the first component acts as a complexing reducing agent and the second component acts as a buffering agent.
  • formate to sulfite are in a molar ratio of 1.5 to 2.5 and the pH of the cleaning solution is 4.3 to 4.7.
  • formate to sulfite in a molar ratio of 3.0 to 4.2 before and the pH of the cleaning solution is 4.1 to 4.5 (claim 2).
  • any compound of the formula M 2 SO 3 is suitable as the alkali metal sulfite
  • any compound of the formula HC (O) OM is suitable as the alkali metal formate, where M is one of the nonradioactive alkali metals (Li, Na, K, Rb, Cs).
  • M is one of the nonradioactive alkali metals (Li, Na, K, Rb, Cs).
  • Na sodium
  • K potassium
  • Na 2 SO 3 is one of the sulfites used by the food industry as a food additive; Na 2 SO 3 is approved under the European approval number E 221 in the additive classes of antioxidants and preservatives.
  • the proportions of the individual components in the aqueous cleaning solution should be chosen so that the molar ratio of formate to sulfite in the range of 1.5 to 4.2, and in particular is about 3.0 to 4.2.
  • the pH of the cleaning solution should be adjusted to a value in the range from 4.0 to 4.8, in particular to pH 4.1 to 4.5. This ensures that the electrochemical potential of the solution remains stable in the range of -225 to -320 mV. A negative potential of this magnitude means that there is a sufficiently strong reduction effect for the desired derouging effect. It has been found that the optimum pH depends somewhat on the type of process: in the dipping process, a pH of about 4.5 is preferred, while in the spraying process a somewhat low pH of about 4.1 is advantageous.
  • Reactions 1 to 3 initially lead to the formation of sulfurous acid. Thereafter, the sulfurous acid decomposes according to the reaction system 4 to the gas hydrate SO 2 * H 2 O, which is well soluble at room temperature and thus prevails in the equilibrium system.
  • the actual derouging is then based on the reduction of iron (III) to iron (II) and associated oxidation of sulfur (IV) to sulfur (VI) according to reaction 5 and subsequent dissolution of the resulting iron (II) hydroxide by the action of formic acid according to reaction 6 and sodium formate according to reaction 7.
  • Another aspect of the invention relates to the use of the inventive cleaning solution for removing Rougingbelägen on media-contacting surfaces of stainless steels selected from the group of chromium / nickel and chromium / nickel / molybdenum steels (claim 5).
  • Rougingbeläge can be removed with the inventive cleaning solution already at room temperature. In other situations, however, it is necessary to work at elevated temperature, which however should be limited to about 80 ° C for both safety reasons and to avoid rapid loss of effect due to evaporating formic acid.
  • the cleaning solution can be effectively used in a very broad concentration range.
  • the sulfite concentration may range from 0.05 to 1.5 mol / kg (claim 4).
  • the sulfite concentration is 0.1 to 1 mol / kg, preferably 0.3 to 0.5 mol / kg.
  • the use of the aqueous cleaning solution for removing Rougingbelägen with a layer thickness of 0.1 .mu.m to 10 .mu.m (claim 6).
  • the cleaning solution according to the invention can be prepared by adding the required amounts of alkali metal sulphite and alkali metal formate to an aqueous receiver and adjusting the required pH by means known per se.
  • the pH can be adjusted by addition of formic acid and / or an alkali metal hydroxide.
  • concentrated aqueous formic acid in the present case is to be understood as meaning an aqueous solution of formic acid having a concentration of at least 50 to approximately 95% by weight. If required, this can be prepared from highly concentrated, ie approximately 100%, formic acid. The order of additions is mandatory because of side reactions of SO 3 2- and because of the solubility of the individual components. It is understood that in the production process according to the invention the addition of the alkali hydroxide and of formic acid corresponds to the seemingly simpler addition of alkali metal formate. With regard to the production process, it has been found that the method according to the invention is comparatively inexpensive and simple.
  • sodium hydroxide NaOH
  • the initially introduced aqueous sodium hydroxide solution has a concentration of 0.9 to 1.1 mol / kg and the added aqueous formic acid has a concentration of 80 to 100 wt .-%, preferably about 85 wt .-% (claim 9).
  • the ready-to-use cleaning solution can be prepared and stored in advance, wherein heating of the cleaning solution, for example by sunlight, is to be avoided in order to avoid an undesirable loss of effectiveness.
  • the admixing of the third amount immediately before use made (claim 10).
  • the precursor thus prepared is readily storable and also no hazardous substance.
  • the completion of the cleaning solution can then take place immediately before use and preferably at the site.
  • Example 2 or 3 the solution obtained after addition of sodium sulfite is stored with a pH of about 6 in suitable containers as a precursor. Immediately before the cleaning process, the required amount of precursor is weighed at the site and then the required amount of aqueous formic acid to adjust a pH of 4.5 to 4.1 (depending on the type of process, see Example 4) mixed. Thus, the cleaning solution is ready for use.
  • a cleaning solution of pH 4.5, with an exposure time of 2 hours at a treatment temperature of 70 ° C and an exposure time of 1 hour at a treatment temperature of 80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (10)

  1. Solution de nettoyage aqueuse destinée à permettre d'éliminer des dépôts de rouging sur des surfaces en contact avec des milieux d'aciers inoxydables, renfermant un premier composant et un second composant, caractérisée en ce que
    le premier composant est un sulfite alcalin et le second composant est un formiate alcalin, les concentrations de ces composants étant ajustées de sorte que le rapport molaire formiate/sulfite soit égal à 1,5 à 4,2, et que le pH de la solution de nettoyage soit égal à 4,0 à 4,8.
  2. Solution de nettoyage aqueuse conforme à la revendication 1,
    dans laquelle le rapport molaire formiate/sulfite est égal à 3,0 à 4,2 et le pH de la solution de nettoyage est égal à 4,1 à 4,5.
  3. Solution de nettoyage aqueuse conforme à la revendication 1 ou 2,
    dans laquelle le sulfite alcalin est du sulfite de sodium et le formiate alcalin est du formiate de sodium.
  4. Solution de nettoyage aqueuse conforme à l'une des revendication 1 à 3,
    dans laquelle la concentration en sulfite est égale à 0,05 à 1,5 mol/kg de préférence à 0,1 à 1 mol/kg, en particulier à 0,3 à 0,5 mol/kg.
  5. Utilisation d'une solution de nettoyage aqueuse conforme à l'une des revendications 1 à 4,
    pour éliminer des dépôts de rouging sur des surfaces en contact avec des milieux d'aciers inoxydables choisis dans le groupe des aciers nickel/chrome et des aciers molybdène/nickel/chrome.
  6. Utilisation conforme à la revendication 5,
    dans laquelle les dépôts de rouging ont une épaisseur de couche de 0,1µm à 10µm.
  7. Procédé de préparation d'une solution de nettoyage aqueuse conforme à l'une des revendications 1 à 4,
    selon lequel on se procure tout d'abord une solution aqueuse d'un hydroxyde alcalin, on mélange ensuite celle-ci avec une première quantité d'acide formique aqueux concentré en excès de façon à ajuster un pH de 3,5 à 4,5, puis on y ajoute une seconde quantité de sulfite alcalin solide conformément à la concentration en sulfite devant être ajustée, un pH de 5,5 à 6,5 s'établissant, et enfin, on ajoute une troisième quantité d'acide formique aqueux concentré jusqu'à atteindre un pH de 4,0 à 4,8.
  8. Procédé conforme à la revendication 7,
    selon lequel l'hydroxyde alcalin est de l'hydroxyde de sodium et le sulfite alcalin est du sulfite de sodium.
  9. Procédé conforme à la revendication 8,
    selon lequel la solution aqueuse d'hydroxyde de sodium de départ a une concentration de 0,9 à 1,1 mol/kg et l'acide formique aqueux ajouté a une concentration de 80 à 100% en poids de préférence d'environ 85% en poids.
  10. Procédé conforme à l'une des revendications 7 à 9,
    selon lequel l'ajout de la troisième quantité est effectué immédiatement avant l'utilisation.
EP16769870.3A 2015-08-19 2016-08-19 Solution de nettoyage aqueuse destinée à éliminer rouging sur des surfaces en contact avec le fluide d'aciers inoxydables, son utilisation et son procédé de fabrication Active EP3337916B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI201630387T SI3337916T1 (sl) 2015-08-19 2016-08-19 Vodna čistilna raztopina za odstranjevanje rouging oblog na površinah nerjavnih jekel, ki so v stiku s sredstvi, uporaba le-te in postopek za njeno izdelavo

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15181647 2015-08-19
PCT/EP2016/069742 WO2017029405A1 (fr) 2015-08-19 2016-08-19 Solution aqueuse de nettoyage pour l'élimination de dépôts de rouille rouge ("rouging") sur des surfaces d'aciers inoxydables en contact avec des milieux, utilisation de celle-ci et son procédé de préparation

Publications (2)

Publication Number Publication Date
EP3337916A1 EP3337916A1 (fr) 2018-06-27
EP3337916B1 true EP3337916B1 (fr) 2019-06-12

Family

ID=53938184

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16769870.3A Active EP3337916B1 (fr) 2015-08-19 2016-08-19 Solution de nettoyage aqueuse destinée à éliminer rouging sur des surfaces en contact avec le fluide d'aciers inoxydables, son utilisation et son procédé de fabrication

Country Status (7)

Country Link
US (3) US20180371379A1 (fr)
EP (1) EP3337916B1 (fr)
JP (1) JP2018525535A (fr)
CN (1) CN108474122A (fr)
DK (1) DK3337916T3 (fr)
SI (1) SI3337916T1 (fr)
WO (1) WO2017029405A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023168467A1 (fr) * 2022-03-11 2023-09-14 Henkel Bet Holding Gmbh Procédé d'élimination de dépôts d'oxyde de fer

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US4789406A (en) 1986-08-20 1988-12-06 Betz Laboratories, Inc. Method and compositions for penetrating and removing accumulated corrosion products and deposits from metal surfaces
AU4148797A (en) * 1996-11-13 1998-06-03 Ashland Inc. Liquid metal cleaner for an aqueous system
GB9909724D0 (en) * 1998-09-25 1999-06-23 Macgregor Keith M Medical cleaning compositions
CN100503800C (zh) * 2006-06-05 2009-06-24 太仓市宝马环境工程有限公司 单乙醇胺再生器清洗剂及其制备方法
US8192550B2 (en) * 2008-02-01 2012-06-05 Ateco Services Ag Use of an aqueous neutral cleaning solution and method for removing rouging from stainless steel surfaces
EP2090676A1 (fr) * 2008-02-01 2009-08-19 Ateco Services AG Procédé destiné l'enlèvement de couches et de dépôts
EP2285944B1 (fr) * 2008-05-14 2013-03-13 Novozymes A/S Compositions de detergents liquides
US9029313B2 (en) * 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
JP5721888B1 (ja) * 2014-07-04 2015-05-20 三菱日立パワーシステムズ株式会社 化学洗浄方法及び化学洗浄装置
US9617502B2 (en) * 2014-09-15 2017-04-11 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid

Non-Patent Citations (1)

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023168467A1 (fr) * 2022-03-11 2023-09-14 Henkel Bet Holding Gmbh Procédé d'élimination de dépôts d'oxyde de fer

Also Published As

Publication number Publication date
US20180371379A1 (en) 2018-12-27
EP3337916A1 (fr) 2018-06-27
JP2018525535A (ja) 2018-09-06
US20240209291A1 (en) 2024-06-27
DK3337916T3 (da) 2019-09-23
CN108474122A (zh) 2018-08-31
US20220056381A1 (en) 2022-02-24
SI3337916T1 (sl) 2019-11-29
WO2017029405A1 (fr) 2017-02-23

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