EP2122011A1 - Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rugueuses sur des aciers inoxydables - Google Patents

Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rugueuses sur des aciers inoxydables

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Publication number
EP2122011A1
EP2122011A1 EP09705741A EP09705741A EP2122011A1 EP 2122011 A1 EP2122011 A1 EP 2122011A1 EP 09705741 A EP09705741 A EP 09705741A EP 09705741 A EP09705741 A EP 09705741A EP 2122011 A1 EP2122011 A1 EP 2122011A1
Authority
EP
European Patent Office
Prior art keywords
acid
cleaning solution
use according
salts
steels
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09705741A
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German (de)
English (en)
Other versions
EP2122011B1 (fr
Inventor
Marc Philippe Vernier
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.)
Ateco Services AG
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Ateco Services AG
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Filing date
Publication date
Application filed by Ateco Services AG filed Critical Ateco Services AG
Priority to EP09705741A priority Critical patent/EP2122011B1/fr
Publication of EP2122011A1 publication Critical patent/EP2122011A1/fr
Application granted granted Critical
Publication of EP2122011B1 publication Critical patent/EP2122011B1/fr
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • 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
    • C11D7/36—Organic compounds containing phosphorus
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • 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 invention relates to methods for removing surface changes which occur on surfaces of stainless metallic materials in the form of coatings and deposits of oxidic iron, in particular on surfaces of stainless steels, as used in process andadosaniagen in the pharmaceutical, food and biotechnology industry frequently used, as well as aqueous cleaning solutions containing a reducing agent and a complexing agent for use in these methods.
  • Process / production equipment used in the manufacture and processing of active pharmaceutical ingredients, pharmaceutical forms, biotechnologically derived active ingredients, foods, etc., as well as systems and equipment used in the manufacture and distribution of these products, as well as systems and equipment, which are operated with ultrapure water, purified water and pure steam, are usually made of stainless steels based on stainless steel alloys. Examples include stirred tanks, storage tanks, storage tanks, fermenters, dryers, Abphili ⁇ anlagen, autoclaves, SferiÜsationsbepuriter, Gefriertrock ⁇ er, washing machines, CIP ⁇ plants, ultrapure water generators, Reinstdampfermaschineer, Verteilieitieux for the media (purified water, ultrapure water, pure steam, products) etc.
  • these surface changes may occur for the first time a few months after commissioning of a system. In other cases, it may take years for such changes to be observed for the first time.
  • This roughening phenomenon is characterized by the appearance of a typical iron oxide or iron hydroxide layer on the surface of the stainless steel material, these typical hematite or magnetite layers containing Cr, Ni and Mo intercalated, indicating a layered Aufiösung tendency of the Edeistahlmaterials.
  • the Rouging Anlagenen are usually between 0.1 - 10 microns, with only the thinner coatings are to be designated as Rougekontaminationen, massive deposits on the other hand correspond more Rostkontaminatio ⁇ en.
  • the cause of rouging is evidently a local depassivation of the chromium oxide protective layer of the Edeistahlober inhabit caused by the breakdown of said protective layer at discrete surface points due to the above parameters, as well as the failure of a sufficient for a repassivation amount of oxygen.
  • This mechanism of local depassivation is favored by the significantly reduced amount of dissolved oxygen in hot waters (WFi> 70 ° C or steam) and by a greatly increased ionic capacity due to the purity of said waters.
  • the elevated temperatures cause iron atoms to diffuse to the surface and react with the oxygen present there to form oxide and hydroxide.
  • EP 1,621,521 and EP 1 300,368 disclose the use of neutral detergents to remove deposits from cold water bearing systems, particularly water supply facilities such as drinking water tanks. Rouging deposits on media-contacting stainless steel surfaces of process / production plants operated with ultrapure water have a different quality than the rust and lime deposits described in the above-mentioned prior art, which occur on blackstones or on non-metallic surfaces, in practice The complete elimination of rouging on stainless steel surfaces has proven to be extremely cumbersome and difficult, leading to popular wisdom that it is imperative to use strong and highly concentrated mineral acids, despite the numerous known disadvantages.
  • Organic acids for example oxalic acid and / or citric acid are also used in part for cleaning off the deposits / deposits.
  • organic acids do not have the digestibility of highly concentrated mineral acids, so often mixtures of organic and inorganic acids are used.
  • complex acid binders eg EDTA or NTA, are added to these acid mixtures.
  • a major drawback of such acid mixtures is that they do not specifically remove the deposits / deposits in the form of oxidic iron compounds, but also partially solubilize the heavy metals contained in the stainless steel alloy. Inappropriate Handling is thus the danger that the Oberfiambae the process /adosanfagen is attacked and thereby adversely affect the surface properties.
  • these cleaning solutions contain after use in the rain! a high Schwermetailanteii, so that the solutions must then be disposed of consuming and professional.
  • grade AISI 304 (* 1.4301), AIS] 304L (1.4307, 1.4306), AlSi 316 (1.4401), AIS 316L (1.4404, 1.4435), AISI 316 Ti (1.4571) and AIS! 904L
  • Cleaning solutions are dissolved, which contain a reducing agent in combination with at least one complexing agent and allow working in the neutral pH range.
  • the present invention relates to a process for the complete removal of oxidic iron compounds Rouging coatings on surfaces, in particular on surfaces in contact with the media, of stainless metallic materials, in particular on media-contacting surfaces of materials made of stainless chromium / nickel steels, in particular of stainless chromium / nickel / molybdenum steels, in particular of stainless chromium / nickel and / or chromium / nickel Grade molybdenum AlSI 304 ( * 1.43 ⁇ 1), AISI 304L (1.4307, 1.4306), AISi 316 (1.4401), AISi 316L (1.4404, 1.4435), AlSI 316 Ti (1.4571) and AISI 904L (1.4539).
  • p .xxxx according to DIN 10027-2]
  • the present invention thus relates to a method for the complete removal of rouging-based surface changes on stainless metallic materials, in particular on media-contacted stainless metallic materials, in particular on materials of stainless chromium / nickel steels of the above quality classes, which is characterized in that said surfaces treated with an aqueous solution containing a reducing agent and at least one Komplexbtldner in the neutral pH range and the said cleaning solutions for use in such a method.
  • a process for the repassivation of selectively destroyed chromium oxide-rich passive layers on stainless steel surfaces, in particular on media-contacting stainless steel surfaces which is characterized in that the Rougingab- deposits formed on said surfaces, with an aqueous solution containing a Reduktionsmitte! and treating at least one complexing agent at neutral pH values and completely removing said deposits and subsequently treating them with an aqueous solution containing an oxidizing agent and preferably at least one complexing agent capable of forming the passivation layer protecting the stainless steel.
  • the present invention further relates to a method for preventing contamination of manufacturing or process products that are produced in process and imperativesanfagen which are made of stainless metallic materials, in particular stainless steels, in particular stainless chrome / nickel! Steels, in particular of stainless chromium / nickel / molybdenum steels, in particular of stainless chrome / nickel! and / or chromium / nickel / molybdenum steels of grade AiSi 304 ( * 1.4301), AISi 304L (1.4307, 1.4306), AISI 316 (1.4401), AISI 316L (1.4404, 1.4435), AISI 316 Ti (1.4571) and AISi 904L ( 1.4539).
  • stainless metallic materials in particular stainless steels, in particular stainless chrome / nickel! Steels, in particular of stainless chromium / nickel / molybdenum steels, in particular of stainless chrome / nickel! and / or chromium / nickel / molybdenum steels of grade
  • the process according to the invention is characterized in particular by treating said process and production plants by means of an aqueous cleaning solution containing a reducing agent and at least one complex binder, removing the changes from the treated surfaces and bringing them into solution, and subsequently removing them from the system together with the cleaning solution be removed.
  • the present invention further relates to the use of an aqueous cleaning solution containing a reducing agent and at least one Kornpiexsentner for removing Rougingbeiägen on surfaces, especially on media wetted surfaces, stainless steels selected from civiler group of chromium / nickel and chromium / nickel / molybdenum steels in the neutral pH range , in particular in a pH range from about pH 4.5 to about pH 9.0, in particular from about pH 6.0 to about pH 8.0, in particular from about pH 6.5 to about pH 7.5.
  • Said Rougingbeläge usually have a layer thickness between 0.1 .mu.m and 10 .mu.m, in particular between 0.4 .mu.m and 0.8 .mu.m.
  • said rouging coating is composed of iron oxide and / or iron hydroxide layers containing Cr and / or Ni and / or Mo embedded therein, wherein said oxidic iron compounds are oxidized iron, in particular Fe (II), Fe (II! And / or Fe (Ii) ZFe (IIi) oxides or hydroxides with constituents of Cr 1 Ni and / or Mo.
  • the steels to be cleaned are those of quality classes AiSI 304 (* 1.4301), AISI 304L (1.4307, 1.4306), AISI 316 (1.4401), AISI 316L (1.4404, 1.4435 ), AIS! 316 Ti (1.4571) and AIS! 904L (1.4539).
  • AiSI 304 (* 1.4301), AISI 304L (1.4307, 1.4306), AISI 316 (1.4401), AISI 316L (1.4404, 1.4435 ), AIS! 316 Ti (1.4571) and AIS! 904L (1.4539).
  • AiSI 304 (* 1.4301), AISI 304L (1.4307, 1.4306), AISI 316 (1.4401), AISI 316L (1.4404, 1.4435 ), AIS! 316 Ti (1.4571) and AIS! 904L (1.4539).
  • the steels to be cleaned are those whose surfaces are exposed to ultrapure water or media-carrying ultrapure water or ultrapure water, wherein said ultrapure water is a. (.. Ph Eur) purified water (Aqua Purif ⁇ cata (AP)) with a conductivity of ⁇ 4.3 .mu.S at 2O 0 C and ⁇ 4.7 .mu.S at 25 0 C (USP 25) is; b. highly purified water (Aqua valde purif ⁇ cata) with a conductivity of ⁇ 2.1 ⁇ S at 25 0 C acts; c.
  • the cleaning solution contains at least 2 different complexing agents as well as optionally an additional substance which has both grain-complexing and reducing properties, e.g. Oxalic acid or one of its salts.
  • Another object of the present invention therefore relates to an aqueous cleaning solution for use in a method for removing Rougingbetägen on media-contacting surfaces of stainless steels selected from the group of chromium / nickel and / or chromium / nickel / molybdenum steels, especially steels of the above grades , in the neutral pH range, characterized in that said cleaning solution contains a reducing agent and at least 2 different Compiexbüdner, and optionally an additional substance which has both complexing and also reducing properties, such as Oxalic acid or one of its salts.
  • the reducing agent used is a salt-like reducing oxygen compound, in particular a reducing oxygen compound selected from the group consisting of sulfur, nitrogen and phosphorus oxygen compounds, in particular a reducing sulfur-oxygen compound, such as, for example. Dithionite or disulfite.
  • an acid is selected as the complexing agent from the group of phosphonic acids, phosphonocarboxylic acids, hydroxyacids, iminosuccinic acids, acetic acids and citric acids or one of them Salts used, in particular a phosphonic acid selected from the group of hydroxyalkane and Alkylenphosphonklaren, in particular a 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), a Aminotri (methylenephosphonic acid) (ATMP), a Hexarnethylendiaminotetra (methylphosphonic) (HDTMP) a Diethyientriamin ⁇ penta (methylenephosphonic acid) (DTPMP) or one of its salts, or a 2-phosphonobutane-1,2,4-tricarboxylic acid or one of its salts.
  • a phosphonic acid selected from the group of hydroxyalkane and Alkylenphosphonklaren, in particular a 1-hydroxyethane-1, 1-diphosphonic acid (HE
  • the complexing agent employed is an iminosuccinylic acid or one of its salts, but in particular an iminodisuccmic acid or one of its salts.
  • the concentration of reducing agent and complexing agent in the cleaning solution to be used according to the invention is in each case in a range from 0.1% by weight to 1% by weight, in particular in a range from 0.2% by weight to 0.8% by weight.
  • a further specific embodiment of the present invention provides the use according to the invention as described herein of an aqueous cleaning solution comprising a reducing agent and at least one complexing agent for avoiding contamination of production or process products which are operated in ultrapure water or media-carrying ultrapure water or with ultrapure (water) steam - And production facilities are made, in particular of contaminants, which are caused by itself from the changed surface detaching particles or constituents, in particular by oxidic Eisenverbtndungs containing particles or constituents, in the context of a process that is characterized in that said surfaces said Process and Praduklamentsanlagen mitteis a reducing agent and at least one KomplexbiJdner containing aqueous cleaning solution treated, the changes of the treated surfaces dissolve, dissolve them and remove them from the system along with the cleaning solution.
  • media in the context of the present invention in the broadest sense ultrapure water and prepared using ultrapure water reaction, nutrient and / or other media-carrying aqueous solutions are understood as in process and Artsäonsanlagen that in the production and Further processing of pharmaceutical agents, pharmaceutical pharmaceutical forms, biotechnologically produced drugs, food, etc., can be used.
  • ultrapure water means highly purified waters which have a conductivity in the range of ⁇ 1.0 ⁇ S and ⁇ 5.0 ⁇ S, measured at a temperature between 20 ° C. and 25 ° C. .
  • AP purified water
  • UDP 25 highly purified water
  • Aqua valde purificata highly purified water with a conductivity of ⁇ 2.1 ⁇ S at 25 ° C, c.
  • pure steam 1 or "steam” refers to water vapor which is used inter alia for sterilization purposes, produced by distilling treated drinking water having a conductivity of ⁇ 5.0 ⁇ S at 25 ° C. or of Aqua Purificata (AP) with a conductivity of ⁇ 2.1 ⁇ S at 25 ° C or ⁇ 4.7 ⁇ S at 25 ° C (USP 25) or highly purified water (Aqua valde purificata) with a conductivity of ⁇ 2.1 ⁇ S at 25 D C or WFI (Water for Injection) with a conductivity of ⁇ 1, 1 ⁇ S at 20 0 C (Ph. Eur.) Or ⁇ 1, 3 ⁇ S at 25 0 C (USP 25), and a conductivity of ⁇ 5.0 ⁇ S having.
  • AP Aqua Purificata
  • Aqua valde purificata Aqua valde purificata
  • structural changes are intended to mean any structural change of stainless metallic surfaces, but especially surfaces of stainless steels, in particular stainless steels selected from the group of chromium / nickel and / or chromium / nickel / molybdenum steels, in particular steels grades AISF 304 (M.4301), aS! 304L (1.4307, 1.4306), AISl 316 (1.4401), AIS! 318L (1.4404, 1.4435), AISI 316 Ti (1.4571) and AISI 904L (1.4539).
  • AISF 304 M.4301
  • aS! 304L (1.4307, 1.4306)
  • AISl 316 1.401
  • AIS! 318L 1.404, 1.4435
  • AISI 316 Ti 1.571
  • AISI 904L (1.4539
  • these are cold-rolled, ground, pickled or electropolished steels of the quality grades with a surface roughness of Ra ⁇ 3.0 ⁇ m.
  • Stainless steels of this steel grade but in particular CrNi or CrNiMo steels of the quality classes AISI 304 ( * 1.4301), AiSI 304L (1.4307, 1.4306), AISI 316 (1.4401), AISI 316L (1.4404, 1.4435), AISI 316 Ti (1.4571) and AISI 904L (1.4539).
  • AISI 304 * 1.4301
  • AiSI 304L (1.4307, 1.4306)
  • AISI 316 1.4307, 1.4306
  • AISI 316 1.4401
  • AISI 316L 1.404, 1.4435
  • AISI 316 Ti 1.571
  • AISI 904L AISI 904L
  • the term "surface changes" is to be understood to mean structural changes in the chromium oxide-rich passive layer of the metallic surface, which are based on the fact that the Cr / Fe ratio is unfavorable to the chromium oxide. Reduced share, whereby the iron can build a new additional iron oxide-rich layer.
  • iron oxide-rich surface In contrast to an intact passive layer, this new iron oxide-rich surface is usually visually recognizable by color changes. The color spectrum ranges from yellow, orange, red, beige, brown, gray to black, but in some cases only after mechanical wiping.
  • oxidic iron or “oxidic iron compounds” are to be understood as meaning iron (III) oxides, iron (III) oxides and iron (II) oxides, such as, for example, Fe 2 O 3 . Fe 3 O 4 , FeO and iron hydroxides or iron (III) oxide hydrates.
  • the latter are a group of substances that can be derived from the iron ([II] oxide and have a different hydration. Examples which its steep at this Fe 2 O 3 3H 2 O 1 2Fe 2 O 3 3H 2 O, Fe 2 O 3 2H 2 O and Fe 2 O 3 H 2 O.
  • the surface changes occurring on said stainless metallic materials are primarily precipitates of oxidic iron compounds, which may occur in the form of fine red-brown particles of iron oxide or iron hydroxide, or in the form of adherent deposits or deposits, the in said particles, deposits or deposits existing oxidische Elsen in the rain! is present as sparingly soluble trivalent Fe (IIi).
  • the particulate surface changes present in a powdery consistency which are easily removed mechanically, for example by wiping
  • the aforementioned coverings and deposits are permanently adhering surface changes that can no longer be removed mechanically.
  • These newly created surface layers can have a color spectrum from Geib, blue, red, brown to black.
  • the surface changes mentioned above include, in particular, the deposits and deposits on stainless metallic surfaces, in particular on surfaces of stainless steels, such as, for example, CrNi or CrNiMo steels, in particular on stainless surfaces made of CrNiMo steels of the quality class of the quality grades, which contain the oxidic iron compounds known under the heading "rouging" AiSi 304 (* 1.4301), AiSI 304L (1.4307, 1.4306), AISI 316 (1, 4401), AlSl 316L (1.4404, 1.4435), AIS! 316 Ti (1.4571) and AlSl 904L (1.4539).
  • AiSi 304 * 1.4301
  • AiSI 304L (1.4307, 1.4306)
  • AISI 316 (1, 4401
  • AlSl 316L 1.404, 1.4435
  • AIS! 316 Ti 1.571
  • AlSl 904L (1.4539.
  • rouging is used interchangeably herein by “rouging” is to be understood a special form of oxide deposits, as occur on Edelstahioberffawaen, in particular surfaces of austenitic stainless steel alloys in hot WFI plant systems or in steam systems, and typically constructed of iron oxide. Iron hydroxide-dominated layers, which typically contain Cr, Ni and Mo or their oxides embedded. These porous and particle-forming iron oxide-rich rouging layers, which generally have a layer thickness between 0.1 and 10 ⁇ m and have the character of a surface corrosion, take the place of the originally present chromium oxide-rich, dense and solid passive layers. Only the thinner coverings can be described as rouge contamination, whereas the more massive coverings, which are also to be observed, are more likely to correspond to rust contamination and represent secondary phenomena independent of the actual roughening phenomenon.
  • Rougingbelag forming substances are primarily iron oxides (FeO, Fe 2 O 3 ) or iron hydroxides, such as Fe (OH) 2 or Fe (OH). 3
  • FeO, Fe 2 O 3 iron oxides
  • iron hydroxides such as Fe (OH) 2 or Fe (OH). 3
  • "Rouging” occurs almost exclusively on surfaces of stainless chromium / nickel steels, particularly stainless steels Chromium / nickel / molybdenum steels, in particular of stainless chromium / nickel / molybdenum steels of the grade AISi 304 ( * 1.4301), AiSI 304L (1.4307, 1.4306), AISI 316 (1.4401), AIS!
  • compounds which have a redox potential which is sufficiently high to reductively dissolve the surface changes, but in particular a redox potential sufficient to convert the Fe (II) which has been oxidically bound in the surface changes into soluble Fe (II), are used as "reducing agents"
  • compounds are used as reducing agents which have a redox potential in the range from -0.4 E7V to -2.0 EW, in particular from -0.5 E7V to -1.5 EW, in particular from -0.6 EW to -1.2 EW, in particular -0.7 EW to -1.0 EW, based on the Normalwassersfoffelektrode measured in a concentration of 1 mol / liter and at a temperature of 25 ° C. All individual numerical values which fall within the abovementioned range from -0.4 E7V to -2.0 E7V, but which are not specifically mentioned here, are likewise to be the subject of the present invention.
  • a salt-like reducing oxygen compound in particular a salt-like reducing inorganic oxygen compound, in particular a compound selected from the group of sulfur, nitrogen and phosphorus oxygen compounds as reduction center! be used in the cleaning solution.
  • inorganic reducing sulfur oxygen compounds are, in particular, sulfite, bisulfite, and dithionite, and their salts, in particular their sodium salts.
  • Such complexing agents which can be used in a specific embodiment of the process according to the invention are acids selected from the group consisting of the phosphonic acids, hydroxyacids, carboxylic acids, iminosuccinylic acids, acetic acids and citric acids or one of their salts.
  • the present invention is based on the surprising finding that it is possible by the combined use of acting as a reducing agent or as Kompiexbifdner compounds in an aqueous Re ⁇ n Trentsiösung complete removal of surface changes on stainless metallic materials.
  • These surface changes are, in particular, oxidized iron compounds which form on metallic surfaces, in particular on metallic surfaces of red-free materials.
  • These stainless materials are, for example, stainless steels, in particular stainless steels with a Cr-Ni steel grade, in particular a Cr-Ni-Mo steel grade, which have good corrosion resistance due to the molybdenum content and improved mechanical properties at high temperatures Relationship to other steel grades without molybdenum.
  • reducing agents in particular inorganic reducing agents, can be used in the cleaning agents which can be used to remove these surface changes.
  • used in neutral aqueous solution have a great ability to disintegrate against oxidic iron compounds, especially against oxidic iron compounds from sparingly soluble trivalent trivalent Fe (ili).
  • redox potential which lies in a range between about -0.4 E ° / V to -2.0 E 0 A /, in particular from -0.5 E 0 A / to -1.5 E 0 A /, in particular from -0.6 EW to -1.2 E7V, in particular from -0.7 EW to -1.0 E7V, measured in relation to the normal hydrogen electrode in a concentration of 1 moi / liter and at a temperature of 25 ° C.
  • inorganic reducing agents are used! but especially salt-like, reducing inorganic oxygen compound including, but not limited to, reducing oxygen compound selected from the group of sulfur, nitrogen and phosphorus oxygen compounds for use.
  • reducing oxygen compound selected from the group of sulfur, nitrogen and phosphorus oxygen compounds for use.
  • examples of inorganic reducing nitrogen oxygen compounds are, in particular, nitrite. Hydrazine can also be used as a reducing agent.
  • the reducing agents used are in particular reducing sulfur oxygen compounds, such as e.g. Dithionite and / or disulfite and / or sulfite and / or bisulfite and / or thiosulfate.
  • the predominantly Fe (1H) -containing deposits / deposits are converted with the reduction of Fe (III) into the more easily complexable Fe (Ij) and thus dissolved and / or converted into colorless crusts, which are more easily blasted off than the original deposits / deposits.
  • Dithionitic solutions and dissolution solutions or mixtures of these solutions are thus similarly effective as mixtures of hydrochloric acid and inhibitors or other inorganic or organic acids. Due to the pH neutral
  • Container surfaces are present, removed, bringing their life and their
  • Sulfate is toxicologically and ecologically unproblematic.
  • technical chemicals are dithionite and pyrosulfite, i.a. as sodium dithionite or as sodium disulfite
  • Dithionate and disulfite in carrying out the inventive method are also salts of reducing acidic nitrogen oxygen compounds, eg. B.
  • Nitrite, or reducing acidic phosphorus oxygen compounds e.g. As phosphites or hypophosphites to call. Hydrazine can also be used as a reducing agent.
  • the invention further relates to the use of certain known per se
  • Complexing agents capable of forming complexes with higher valent metal ions, but especially with Fe (Ui) and in particular Fe (II).
  • the Kompiex clay applicable in the context of the present invention should also be inert to the reducing effect of the reducing agent present in the treatment solution under the prevailing conditions there or have a Kurzzeitstabiftician against said reducing agents, which is sufficient to the full functionality of said reducing agent said time To guarantee compiled biologists.
  • Treatment has already begun, but in particular at least 10 minutes, preferably at least 20 minutes, preferably at least 30 minutes and up to 1 hour after the start of treatment.
  • the complexing agent may also be consumed or consumed by the
  • Such complexing agents which can be used in a specific embodiment of the process according to the invention are acids selected from the group of phosphonic acids, hydroxy acids, carboxylic acids,
  • HEDP Hydroxyethane-1,1-diphosphinic acid
  • ATMP aminotri (methylenephosphonic acid)
  • HDTMP H-oxamethylenediamino-tetra (methylphenyl acid)
  • DTPMP diethylenetriaminopenta (methylenephosphite) phosphonic acid)
  • succinylic acid groups optionally in salt form, such as, for example, fminosuccinic acid, but in particular iminodisuccinic acid.
  • Granulizers may be employed, but are not limited to compounds of the hydroxy (poly! Y) carboxylic acid type, in particular
  • Hydroxypolycarboxylic acids with 2-4 Carb ⁇ xyl phenomenon such as Citric acid, tartaric acid or apidic acid or one of their salts.
  • ISDA ethylenediaminetetraacetic acid
  • PDTA propylenediaminetetraacetic acid
  • NTA Nitrilotriacetic acid
  • Phosphonobutane 2,4-t-carboxylic acid or one of its salts.
  • Ethanoidigiycin be used as a complexing agent.
  • the salts which can be used in the cleaning solutions described above are primarily the alkali metal salts of those mentioned therein
  • Acids in particular their lithium, sodium, potassium, rubidium and
  • Cesium salts but especially their sodium and potassium salts.
  • the presence of the complexing agents prevents the reaction of the oxidic iron with the reducing agent to lead to the formation of crusts. It was found that the complexing agents significantly improve the stripping process of the constituents of the oxidic iron from the stainless metal surface.
  • Cleaning solution used which contain a combination of reducing agent and at least one, but especially two or more Compiexbüdner belonging to different classes of substances and optionally a buffer.
  • said aqueous pure solution may additionally comprise further constituents selected from the group of buffer salts, wetting agents, stabilizers and / or further reducing agents which may be dissolved, emuligated or incorporated as suspended solids.
  • the process according to the invention is carried out in a pH range from about 4.Q to about 10.0, in particular from about 4.5 to about 9.5, in particular from about 6.0 to about 8.0, in particular from about 6.5 to about 7.5.
  • the cleaning solution is usually also added buffer, in particular buffers based on harmless Saize of weak mineral acids.
  • buffers based on harmless Saize of weak mineral acids.
  • Suitable buffer systems for setting a desired pH can be taken from relevant chemical reference works.
  • the system bicarbonate / carbonic acid is well suited.
  • other buffer systems can also be used. It has also been found that the effect of an aqueous cleaning solution containing a reducing agent, i. in particular dithioite or disulfite or a combination of dithionite and disulfite, and at least one, but especially at least two, complexing agents, i.
  • the chemical components required for carrying out the process according to the invention can be introduced into the aqueous cleaning solution in any suitable form, ie as separate or premixed solids, as solutions and concentrates or as pastes or gels.
  • the preparation of the cleaning solution can be carried out prior to its snaking contacts with the deposits to be treated, but the cleaning solution can also be prepared in situ in the equipment to be treated, eg in a production container or in a piping system, by adding the individual components at different times.
  • the reducing agent and the complexing agent can, as indicated, be added to the cleaning solution in advance or in situ, these in each case in a concentration range from 0.025% by weight to 25% by weight, in particular in a concentration range of 0.05% by weight. % to 15 wt .-%, in particular in a concentration range of 0.1 wt .-% to 10 wt .-%, in particular in a Konzentratio ⁇ s Quarry of 0.2 wt .-% to 5 wt .-%, in particular in a Ko ⁇ zentrations Highway from 0.25 wt .-% to 1 wt .-%, in particular in a concentration range of 0.25 wt .-% to 0.5 wt .-%, in particular in a Konzentratäons Suite from 0.5 wt .-% to 1.5 wt. % in the cleaning solution.
  • a cleaning solution which has a reducing agent such as dithionite or disulfite or a combination of dithionite or disulfite or one of its salts and at least contains one, but preferably at least two k ⁇ mplexbüdende substances, such as phosphonic acid and / or a compound containing Succinylklare phenomenon, or one of its salts.
  • a reducing agent such as dithionite or disulfite or a combination of dithionite or disulfite or one of its salts
  • a reducing agent such as dithionite or disulfite or a combination of dithionite or disulfite or one of its salts
  • a cleaning solution which comprises dithionite or disulphite or a combination of dithionite or disulphite or one of its salts as inorganic reducing agent! and a phosphonic acid and a compound containing succinylic acid groups, or one of their salts, as a complexing agent.
  • the cleaning solution consists of dithionite or one of its salts and a combination of phosphonic acid and iminosuccinic acid, or one of its salts, and optionally a buffer.
  • the cleaning solution consists of dithionite or one of its salts and a combination of phosphonic acid and iminosuccinic acid, or one of its salts, and oxalic acid or one of its salts, and optionally a buffer.
  • the phosphonic acid mentioned above is a phosphonobufanetricarboxylic acid or one of its salts
  • iminosuccinic acid is an iminodisuccinylic acid or one of its salts.
  • the reducing agent and the complexing agent are present in a concentration ratio of 0.7% reducing agent / 1.0% complexing agent, in particular in a concentration ratio of 0.3% reducing agent / 0.5% of complexing agent, if the cleaning solution contains only one complexing agent or in a concentration ratio of 3% reducing agent / 8% of complexing agent, in particular 0.5% reducing agent / 1.5% Kompfexsent ⁇ er, in particular 0.6% reducing agent / 1.1% Komplexbüdner, in particular 0.25% reducing agent / 0.75% Komplexbiidner, in particular in a concentration ratio of 0.3% reducing agent / 0.6% complexing agent, if the cleaning solution contains two different complexing agents.
  • the cleaning solution may additionally contain between 0.01% and 0.5%, in particular between 0.04% and 0.2%, in particular between 0.05% and 0.1%, of a compound which has both complexing and reducing properties.
  • the treatment of oxidic E ⁇ sentressen containing deposits and deposits on stainless metallic surfaces, in particular on surfaces of stainless steels, preferably takes place in a temperature range of about 20 p C to about 98 ° C, in particular in a temperature range from about 40 0 C to about 90 0 C.
  • the inventive method is designed so that the stainless metallic surfaces, in particular the surfaces of stainless steels, depending on the strength and extent of the deposits, for a period of about 30 minutes to 12 hours, in particular for a period of 60 minutes 8 hours, in particular for a period of 1.5 to 6 hours, in particular for a period of 2 to 5 hours, in particular for a period of 3 to 4 hours, in particular for a period of 1, 5 to 2 hours in contact with the aqueous cleaning solution stay.
  • the stainless metallic surfaces to be cleaned are located in process and / or production plants, in particular in process and / or production plants, which contribute ultrapure water and / or ultrapure steam, in particular hot ultrapure water and / or pure steam Temperatures of more than 60 0 C, operated.
  • the containers and devices to be cleaned are filled with the cleaning solution according to the invention and the pH is adjusted within a range from pH 4.0 to pH 8.0, in particular in a range from pH 6.0 to pH 8.0.
  • the cleaning solution can be used, for example, by using the stirring or flow in the containers. or by using external circulation pumps are moved through the system, with slow Riess devisen are preferred.
  • Methylene blue solution can be easily checked for sufficient amounts
  • Reducing agent present in the cleaning solution If this is the case, it results in a clearly visible discoloration of the methylene blue solution. On the other hand, is the concentration of reduction center! suboptimal, the methylene blue is not decolorized and it may be necessary to add reducing agent.
  • the endpoint of a purification process may be determined by means of iron impact measurements (e.g., coiorimetric). If the iron content in the cleaning solution reaches a stable value after a certain exposure time, the cleaning process can be ended.
  • iron impact measurements e.g., coiorimetric
  • the cleaning solution is removed and the cleaned containers and
  • Repassivation of the stainless steel surfaces can (such as HNO 3; ⁇ 20 ppm Cl "or Wasserstoffperxoid) by means of an aqueous solution containing an oxidizing agent, in particular an oxygen-donating acid, soft capable the stainless steel build protective passive layer and optionally at least one
  • Oxygen-containing ultrapure water in particular of oxygen-containing ultrapure water having a conductivity of 0.5 .mu.S / cm and at a temperature of 10 0 C - 20 0 C, in particular from 12 ° C to 15 ° C, preferably at 14 ° C are performed.
  • the ultrapure water used contains the natural load of dissolved O 2 according to the preparation, the necessary chromium oxide-rich passive layer can be built up.
  • Has achieved value This value is preferably ⁇ 0.7 ⁇ S / cm.
  • coverings / deposits of items eg. B. individual pieces of pipe or
  • Fittings to be removed, which are taken from the plant or device can, the process of the invention can also be carried out so as to put the disassembled parts to be liberated by the Befägen / deposits in a bath of a cleaning solution according to the invention.
  • Particularly good cleaning results can also be obtained by spraying (via, for example, spray balls, C (leaning) i (n) P (Iace) sprayers), which is preferably felt under an inert atmosphere and also constituents! of the present invention.
  • Inert reaction conditions can be achieved by gassing the systems to be cleaned with inert gases, e.g. Nitrogen or noble gases, hersteiien.
  • Also included in the present invention is a cleaning solution for use in the process of the invention having the composition disclosed hereinbefore.
  • Tubes made of stainless steel (AiSi 316L), which are made of a pharmaceutical
  • Piping system for the distribution of hot ultrapure water come and are treated with a strong oxidic iron layer (rouging).
  • the oxidic iron layer (rouging) in this example consists predominantly chemically of sparingly soluble Fe (! I [) compounds.
  • Phosphonobutane 1,2,4-tricarboxylic acid sodium salt PBTC-Na4
  • 3% tetrasodium iminodisuccinate 1% of a sodium bicarbonate / carbonic acid buffer is used.
  • a further improvement of the result can be achieved by adding about 0.5% potassium oxalate to the abovementioned difhionite solution.
  • Stainless steel tubes (AiSl 316L), which are made of a pharmaceutical grade
  • Piping system for the distribution of hot ultrapure water (WFi) come and are subjected to a strong oxidic iron layer (rouging).
  • the oxidic iron layer (rouging) in this example consists predominantly chemically of sparingly soluble Fe (Ili) bonds.
  • Tetrasodiumimi ⁇ odisuccinate 0.1% potassium oxalate and 0.2% of a sodium bicarbonate / carbonic acid buffer.
  • Diameter of 7 cm is placed in 250 ml of the above dithionite solution.
  • the solution pH (beginning) about 7.5) at 7O 0 C for 5 h at low
  • Substances / agents used A 300 liter stainless steel batch tank (AISI 316L) is used, which is used in pharmaceutical production and is treated with an oxidic iron layer (rouging).
  • the oxidic iron layer (rouging) in this example consists predominantly chemically of sparingly soluble Fe (III) compounds,
  • methylene blue is suitable for tracking the cleaning process (derouging process) in which one tests a pumped subset at regular intervals.
  • the endpoint of a cleaning process can be determined by means of iron content measurements (e.g., colorimetric). If the iron content in the cleaning solution reaches a stable value after a certain exposure time, the cleaning process can be ended.
  • Substances / agents used A 750 liter stainless steel batch tank (AlSl 316L) with CIP spraying equipment used in pharmaceutical production and with an oxidic iron layer is used
  • the oxidic iron layer (rouging) continues in this example! chemically predominantly from sparingly soluble Fe (lil) compounds together.
  • Phosphonobutane 1, 2,4-tricarboxylic acid sodium salt (PBTC-Na4), 0.25% Tetrasodium inodisuccinate, 0.05% potassium oxalate, 0.1% oxalic acid and 0.1% of a sodium bicarbonate / Kohjenhoffrepuffers used.
  • Experimental procedure The batch tank and the circulating pump pipelines required for the CIP spraying unit are completely purged with gaseous nitrogen. 150 liters of the above-mentioned dithionite solution are poured into the inertized feed tank. The solution (pH (start) approx. 7.5) is circulated over the circulation pump and the pipe lines at 75 ° C for 45 minutes.
  • the container wall is permanently wetted with the dithiological solution via the C! P spray ball. During the entire cleaning time, the preparation tank remains inert with nitrogen. After the cleaning time, 10 ml of the solution are removed and analyzed for their iron content. The container is then rinsed with water and a wipe sample is performed with a white wipe.
  • the oxidic iron layer (rouging) is completely removed.
  • the iron content of the solution after the exposure time is 1.23 mg / L iron.
  • the pH changes slightly during the reaction; pH (end) approx. 7.0.
  • the wipe remains completely white after wiping the container surface.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

L'invention concerne un procédé d'élimination de couches et de dépôt sur des surfaces inoxydables, en particulier sur des surfaces en métal inoxydable utilisées dans les installations de traitement et de production de l'industrie pharmaceutique, de l'industrie alimentaire et de l'industrie biotechnologique, ainsi que des solutions aqueuses de nettoyage qui contiennent un agent réducteur et au moins un agent de formation de complexes destinés à être utilisés dans ce procédé.
EP09705741A 2008-02-01 2009-01-30 Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rouging sur des aciers inoxydables Active EP2122011B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09705741A EP2122011B1 (fr) 2008-02-01 2009-01-30 Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rouging sur des aciers inoxydables

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08150974A EP2090676A1 (fr) 2008-02-01 2008-02-01 Procédé destiné l'enlèvement de couches et de dépôts
EP09705741A EP2122011B1 (fr) 2008-02-01 2009-01-30 Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rouging sur des aciers inoxydables
PCT/EP2009/051074 WO2009095475A1 (fr) 2008-02-01 2009-01-30 Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rugueuses sur des aciers inoxydables

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EP2122011A1 true EP2122011A1 (fr) 2009-11-25
EP2122011B1 EP2122011B1 (fr) 2011-08-24

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EP09705741A Active EP2122011B1 (fr) 2008-02-01 2009-01-30 Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rouging sur des aciers inoxydables

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AT (1) ATE521732T1 (fr)
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CN103911625B (zh) * 2014-04-25 2016-03-16 湖南大学 一种中性除油除锈剂及其制备方法
US20180371379A1 (en) 2015-08-19 2018-12-27 Beratherm Ag Aqueous cleaning solution for removal of rouging deposits on media-contacted surfaces of stainless steels, use thereof and process for production thereof
DE102015114481B4 (de) 2015-08-31 2018-05-09 Nikolay Tzvetkov Tzvetkov Wässrig-neutrale derouging-, entrostungs-, passivierungs- und dekontaminierungslösungen und verfahren zu ihrer verwendung
EP3249076B1 (fr) 2016-05-24 2018-08-22 Technochim SA Produits pour le traitement préventif d'acier inoxydable et procédés associés
CN110408757A (zh) * 2018-04-28 2019-11-05 南京理工大学 一种高强塑性匹配316l不锈钢板材的制备方法
HUE053163T2 (hu) 2018-07-23 2021-06-28 Technochim Sa Eljárás rúzs eltávolítására rozsdamentes acélról
CN110144594A (zh) * 2019-06-18 2019-08-20 雅思汀娜（北京）科技有限公司 一种清洁剂及其制备方法和应用
KR20230024336A (ko) * 2020-06-10 2023-02-20 케메탈 게엠베하 수성 피클링 조성물 및 그의 용도
JP2023530923A (ja) * 2020-06-10 2023-07-20 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング 水性酸洗い組成物及びその使用方法
CN111809189A (zh) * 2020-07-20 2020-10-23 清研高装科技(天津)有限公司 一种水基不锈钢清洗剂及其制备方法
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CH699016B1 (de) 2010-10-29
DK2122011T3 (da) 2011-11-21
EP2090676A1 (fr) 2009-08-19
EP2122011B1 (fr) 2011-08-24
ATE521732T1 (de) 2011-09-15

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