EP2122011B1 - Utilisation d'une solution aqueuse neutre de nettoyage et procédé d'élimination de couches rouging sur des aciers inoxydables - Google Patents

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

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EP2122011B1
EP2122011B1 EP09705741A EP09705741A EP2122011B1 EP 2122011 B1 EP2122011 B1 EP 2122011B1 EP 09705741 A EP09705741 A EP 09705741A EP 09705741 A EP09705741 A EP 09705741A EP 2122011 B1 EP2122011 B1 EP 2122011B1
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Prior art keywords
cleaning solution
aisi
complexing
reducing agent
acid
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German (de)
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EP2122011A1 (fr
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Marc Philippe Vernier
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Ateco Services AG
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Ateco Services AG
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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 deposits and deposits of oxidic iron, in particular on surfaces of stainless steels, as in process and production plants in the pharmaceutical, food and biotechnology industries 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 pharmaceutical forms, biotechnologically produced active ingredients, food, 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, bottling plants, autoclaves, sterilization tanks, freeze dryers, washing machines, CIP plants, ultrapure water generators, pure steam generators, distribution lines for the media (purified water, ultrapure water, pure steam, products) etc.
  • Stainless steels eg CrNiMo steels, grade AISI 316L, AISI 316Ti or AISI 904L
  • Rouging and shipments from typical brown-red particles to the final product or the final product.
  • 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.
  • Said 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 stratified dissolution 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 rather correspond to rust contamination.
  • the cause of the 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 lack of 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 ion-dissolving 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.
  • Such neutral cleaning agents are eg in the US-P 6,310,024 .
  • U.S. Patent 5,587,142 U.S. Patent 4,789,406 described for the cleaning of boilers, water heaters, etc, for the removal of rust and / or limescale deposits.
  • EP 1,621,521 such as EP 1,300,368 discloses the use of neutral detergents to remove deposits from cold water bearing systems, particularly water supply facilities such as drinking water tanks.
  • WO 91/17124 discloses a mixture consisting of a di- or polyphosphonic acid and a reducing agent for the dissolution of metal oxides, in particular for use in the decontamination of radioactive materials.
  • WO 02/10326 describes corrosion control methods and compositions for high strength steels in the presence of a cleaning solution for removing iron oxide deposits on metallic surfaces, particularly in steam generating equipment.
  • the cleaning solution contains 1-hydroxy-ethylidene-1,1-diphosphonic acid, at least ethoxylated or oxidized ethoxylated mercaptan, and at least one benzotnazole or benzimidazole compound.
  • 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.
  • complexing agents for example EDTA or NTA, are added to these acid mixtures.
  • a major disadvantage of such acid mixtures is that they do not specifically remove the deposits / deposits in the form of oxidic iron compounds, but also partially dissolve the heavy metals additionally contained in the stainless steel alloy. Inappropriate Handling is thus the danger that the surface of the process / production equipment is attacked and thereby the surface properties are adversely affected.
  • these cleaning solutions usually contain a high heavy metal content after use, so that the solutions must then be disposed of consuming and professional.
  • the cleaning solutions used in roughening decontamination have been provided with specific additives to mitigate the negative effects of the concentrated mineral acids on the stainless steel surfaces as well as elaborate protocols for process control and control to ensure a minimum residence time of the cleaning solution the stainless steel surfaces with maximum cleaning effect to achieve, as for example in the " Tech- nical Bulletin "by Henkel (Article No. 26 / Rev. 00, 2003 ) is described.
  • the present invention thus relates to a method for the complete removal of surface rouges based on rouging with a layer thickness between 0.1 microns and 10 microns on media-touched stainless metallic materials selected from the group of stainless chromium / nickel and chromium / nickel / molybdenum steels, especially steels above grades, characterized in that said surfaces with an aqueous solution containing 0.25% by weight - 25% by weight of a reducing agent and one or more complexing agents in an amount of 0.2% by weight - 25% by weight containing a phosphonic acid or a salt thereof treated in the neutral pH range, wherein said media-contacting surfaces are those which are exposed to ultrapure water and / or ultrapure (water) vapor and wherein the cleaning solution contains an additional substance which has both complexing and reducing properties, and said cleaning solutions for use in such a process.
  • a further process for the repassivation of selectively destroyed chromium oxide-rich passive layers on stainless steel surfaces, in particular on media-contacting stainless steel surfaces can be used, characterized in that the rouging deposits formed on said surfaces, with an aqueous solution containing a reducing agent and treated at least one complexing agent at neutral pH and said deposits completely removed and then treated with an aqueous solution containing an oxidizing agent and preferably at least one complexing agent, which is able to build up the stainless steel protective passive layer.
  • the application of the inventive method also leads to the avoidance of contamination of manufacturing or process products that are produced in process and production equipment, which are made of stainless metallic materials, in particular stainless steels, especially stainless chromium / nickel steels, in particular stainless chromium / nickel / molybdenum steels, in particular of stainless chromium / nickel and / or chromium / nickel / molybdenum steels of the 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).
  • the present invention further relates to the use of an aqueous cleaning solution in the composition described above for removing rouging deposits on surfaces, in particular on media-contacting surfaces, stainless steels selected from the 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 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 which contain incorporated Cr and / or Ni and / or Mo, said oxidic iron compounds being oxidized iron, in particular Fe (II), Fe (III) and / or Fe (II ) / Fe (III) oxides or hydroxides with constituents of Cr, Ni and / or Mo.
  • the steels to be cleaned are those 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 (1.4401), AISI 316L (1.4404, 1 4435), AISI 316 Ti (1.4571) and AISI 904L (1 4539).
  • the cleaning solution contains at least 2 different complexing agents as well as an additional substance which has both complex-forming and reducing properties, such as, for example, 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 Rougingbelägen with a layer thickness between 0.1 .mu.m and 10 .mu.m on media-contacting surfaces of stainless steels selected from the group of chromium / - nickel and / or chromium / nickel / Molybdenum steels, in particular of steels of the above-mentioned quality classes, in the neutral pH range, characterized in that cleaning solution contains 0.25% by weight - 25% by weight of a reducing agent and at least 2 different complexing agents in an amount of 0.2% by weight - 25% by weight containing a phosphonic acid or a salt thereof, and an additional substance which has both complexing and reducing properties, such as oxalic acid or one of its salts, wherein said surfaces in contact with the media are those which are exposed to ultrapure water and / or ultrapure (water) vapor.
  • stainless steels selected from the group of chromium /
  • 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, e.g. Dithionite or disulfite.
  • the complexing agent used is an acid selected from the group of phosphonic acids, or one of its salts, in particular a phosphonic acid selected from the group of hydroxyalkanoic and alkylenephosphonic acids, in particular a 1-hydroxyethane-1,1-diphosphonic acid (HEDP ), an aminotri (methylenephosphonic acid) (ATMP), a hexamethylenediaminotetra (methylenephosphonic acid) (HDTMP), a diethylenetriaminopenta (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 hydroxyalkanoic and alkylenephosphonic acids, in particular a 1-hydroxyethane-1,1-diphosphonic acid (HEDP ), an aminotri (methylenephosphonic acid) (ATMP), a hexamethylenediaminotetra (methylenephosphonic acid) (
  • Another complexing agent which may be used is a phosphonocarboxylic acid, hydroxy acid, iminosuccinylic acid, acetic acid or citric acid, in particular an iminosuccinylic acid or one of its salts, but in particular an iminodisuccinylic acid or one of its salts.
  • the concentration of reducing agent and complexing agent in the cleaning solution to be used may each be in a range of 0.1 wt% to 1 wt%, more preferably in a range of 0.2 wt% to 0.8 wt% ,
  • an aqueous cleaning solution containing a reducing agent and at least one complexing agent to prevent contamination of manufacturing or process products, which in with ultrapure water or media-producing ultrapure water or process and production plants operated with ultrapure (water) steam, in particular of contaminations which are caused by particles or constituents which detach from the changed surface, in particular by particles or constituents containing oxidic iron compounds
  • Process characterized in that said surfaces of said process and production plants by means of a reducing agent and at least one complexing agent containing aqueous cleaning solution that removes changes from the treated surfaces, this brings into solution and together with the cleaning solution from the system away.
  • media in the context of the present invention in the broadest sense ultrapure water as well as produced using ultrapure water reaction, nutrient and / or other media-carrying aqueous solutions are understood, as in process and production equipment used in the production and Further processing of pharmaceutical agents, pharmaceutical pharmaceutical forms, biotechnologically produced drugs, food, etc., can be used.
  • pure steam or “ultra pure (water) steam” is meant water vapor which i.a. used for sterilization purposes, prepared by the distillation of treated drinking water with 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 ° C or WFI (Water for Injection) with a conductivity of ⁇ 1.1 ⁇ S at 20 ° C (Ph. Eur.) Or ⁇ 1.3 ⁇ S at 25 ° C (USP 25) and having a conductivity of ⁇ 5.0 ⁇ S.
  • AP Aqua Purificata
  • WFI Water for Injection
  • surface modifications in the most general embodiment means 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 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) grades.
  • 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) grades.
  • these are cold-rolled, ground, pickled or electropolished steels of the mentioned 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 (1.4401), AISI 316L (1.4404, 1.4435), AISI 316 Ti (1.4571) and AISI 904L (1.4539).
  • the term "surface changes" is understood to mean structural changes of the chromium oxide-rich passive layer of the metallic surface, which are based on the fact that the Cr / Fe ratio is too low Reduces chromium content, which allows the iron to build up a new additional iron oxide-rich 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 (II, III) oxides and iron (II) oxides, such as 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 ferric oxide and have a different hydration. Exemplified at this point Fe 2 O 3 3H 2 O, 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 As a rule, oxidic iron present in said particles, deposits or deposits is present as sparingly soluble trivalent Fe (III).
  • oxidic iron present in said particles, deposits or deposits is present as sparingly soluble trivalent Fe (III).
  • the aforementioned coverings and deposits are permanently adherent surface changes that can not be mechanically removed.
  • the aforementioned surface changes include, in particular, the deposits and deposits on oxidic iron surfaces known under the heading "rouging" on stainless metallic surfaces, in particular on surfaces of stainless steels, such as e.g. CrNi or CrNiMo steels, in particular on stainless surfaces of CrNiMo steels of quality 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).
  • AISI 304 * 1.4301
  • AISI 304L (1.4307, 1.4306)
  • AISI 316 1.4401
  • AISI 316L 1.4435
  • AISI 316 Ti (1.4571
  • AISI 904L (1.4539.
  • Rouging is to be understood as meaning a special form of oxidic deposits, as occur on stainless steel surfaces, in particular on surfaces of austenitic stainless steel alloys in hot WFI systems or in steam systems, and which are typically constructed of iron oxide or 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
  • reducing agent in particular compounds are used 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 oxidized in the surface changes Fe (III) into soluble Fe (II).
  • the reducing agents used are compounds which have a redox potential in the range from -0.4 E ° / V to -2.0 E ° / V, in particular from -0.5 E ° / V to -1.5 E ° / V, in particular of -0.6 E ° / V to -1.2 E ° / V, in particular from -0.7 E ° / V to -1.0 E ° / V, relative to the normal hydrogen electrode measured in a concentration of 1 mol / liter and at a temperature of 25 ° C.
  • 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, can be used as reducing agent in the cleaning solution.
  • inorganic reducing sulfur oxygen compounds are, in particular, sulfite, bisulfite, and dithionite, and their salts, in particular their sodium salts.
  • complexing agent known, commercially available compounds can be used which are capable of complexing iron ions, in particular iron (II) ions, in solution and, moreover, are inert towards the effect of the reducing agent contained in the cleaning solution or else sufficient have high short-term stability to said reducing agent, so that they can perform their function as a complexing agent for the time required for the cleaning.
  • 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 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 a complexing agent compounds in an aqueous cleaning solution to completely remove surface changes on stainless metallic materials.
  • These surface changes are, in particular, oxidic iron compounds which form on metallic surfaces, in particular on metallic surfaces of red-free materials.
  • the stainless materials mentioned 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 owing to the molybdenum content and improved high-temperature mechanical properties Relation to other steel grades without molybdenum.
  • reducing agents which can be used to remove these surface alterations are reducing agents, in particular inorganic reducing agents which, in neutral aqueous solution, have a great disintegration power over oxidic iron compounds, in particular with respect to oxidic iron compounds from sparingly soluble oxidic trivalent Fe (III).
  • said reducing agents have a redox potential ranging from about -0.4 E ° / V to -2.0 E ° / V, in particular from -0.5 E ° / V to -1.5 E ° / V, in particular -0.6 E ° / V to -1.2 E ° / V, in particular from -0.7 E ° / V to -1.0 E ° / V, relative to the normal hydrogen electrode measured in a concentration of 1 mol / liter and at a temperature of 25 ° C.
  • the inorganic reducing agents used are in particular salt-type, reducing inorganic oxygen compounds including, but not limited to, reducing oxygen compound selected from the group of sulfur, nitrogen and phosphorus oxygen compounds.
  • inorganic reducing nitrogen oxygen compounds mention may be made in particular of nitrite. Hydrazine can also be used as a reducing agent.
  • Reducing agents used in the process described herein are, in particular, reducing sulfur oxygen compounds, e.g. Dithionite and / or disulfite and / or sulfite and / or bisulfite and / or thiosulfate.
  • the predominantly Fe (III) -containing deposits / deposits are converted with the reduction of Fe (III) in the easier complexing Fe (II) and so dissolved and / or converted into colorless crusts, which are more easily blasted than the original deposits / deposits.
  • Dithionite solutions and disulfite solutions or mixtures of these solutions are thus similarly effective as mixtures of hydrochloric acid and inhibitors or other inorganic or organic acids.
  • the agents according to the invention can also be used without restriction for the treatment of stainless steels. Coats of oxidic iron compounds are thus protected by the inventive composition gently from metal surfaces of stainless steel, as z. B. present in process and production facilities including lines or Se graviterober lake removed, bringing their life and their function can be significantly increased.
  • the risks during transport and use of the inventive cleaning solution or its components are significantly lower than when using hydrochloric acid and / or other inorganic or organic acids.
  • the final sulfate formed in the reaction with the oxidic iron compounds is toxicologically and ecologically unproblematic.
  • technical chemicals are dithionite and pyrosulfite, i.a. as sodium dithionite or as sodium disulfite (sodium pyrosulfite), inexpensive to buy and therefore economical to use.
  • reducing sulfur compounds dithionite and disulfite in carrying out the method described herein are also salts of reducing acidic nitrogen oxygen compounds, eg. As nitrite, or reducing acidic phosphorus oxygen compounds, for.
  • reducing acidic nitrogen oxygen compounds eg. As nitrite, or reducing acidic phosphorus oxygen compounds
  • phosphites or hypophosphites to call. Hydrazine can also be used as a reducing agent.
  • a dithionite or disulfite or a combination of dithionite and disulfite may be used in the cleaning solution. It has also been found that the effect of the reducing agent, ie in particular the dithionite / disulfite, in the sense of removal of the iron oxide Deposits / deposits is improved when the cleaning solution also one or more complexing agents are added.
  • the invention further relates to the use of certain complexing agents which are known per se and which are capable of forming complexes with higher-valent metal ions, but especially with Fe (III) and in particular Fe (II).
  • the complex images which can be used in the context of the present invention should furthermore be inert to the reducing action of the reducing agent present in the treatment solution under the conditions prevailing there or have short-term stability with respect to said reducing agents, which is sufficient to ensure full functionality for the period of the treatment Guarantee complexing agent.
  • the complexing agent is added to the cleaning solution with a time delay after the 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 after it is consumed or impaired by the action of the reducing agent in its action, can be replaced by the addition of fresh complexing during the cleaning process.
  • 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 phosphonic acids, hydroxyacids, carboxylic acids, iminosuccinylic acids, acetic acids and citric acids or one of their salts.
  • compounds which contain phosphonic acid groups if appropriate in salt form, such as, for example, hydroxyalkanephosphonic acid or one of its salts, but in particular 1-hydroxyethane-1,1-diphosphonic acid, may be mentioned here by way of example (HEDP) or an alkylenephosphonic acid, but especially aminotri (methylenephosphonic acid) (ATMP), hexamethylenediaminotetra (methylenephosphonic acid) (HDTMP) or diethylenetriaminopenta (methylenephosphonic acid) (DTPMP) and / or compounds which Succinylklare phenomenon, optionally in salt form, such as iminosuccinyl, but especially iminodisuccinic.
  • HEDP hydroxyalkanephosphonic acid or one of its salts
  • 1-hydroxyethane-1,1-diphosphonic acid may be mentioned here by way of example (HEDP) or an alkylenephosphonic acid, but especially aminotri (methylenephosphonic acid) (ATMP), hexamethylenediaminote
  • the phosphonic acid type complexing agents which are known per se, when used for the removal of deposits and deposits on stainless surfaces in pharmaceutical, food and biotechnological plants, have the advantage that they are toxicologically harmless.
  • chelating agents include, but are not limited to, hydroxy (poly) carboxylic acid type compounds, especially hydroxypolycarboxylic acids having 2-4 carboxyl groups, e.g. Citric acid, tartaric acid or malic acid or one of their salts.
  • ISDA isorin-N, N-diacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • PDTA propylenediaminetetraacetic acid
  • NDA nitrilotriacetic acid
  • said complexing agent is thus a carboxylic acid, in particular an aminocarboxylic acid or a phosphonocarboxylic acid, in particular a phosphonotricarboxylic acid, in particular a phosphonobutane tricarboxylic acid, such as e.g. a 2-phosphonobutane-1,2,4-tricarboxylic acid or one of its salts.
  • sodium citrate or ethanoldiglycine can be used as complexing agents in the process according to the invention.
  • the salts which can be used in the cleaning solutions described above are primarily the alkali metal salts of the acids mentioned there, in particular their lithium, sodium, potassium, rubidium and cesium salts, but especially their sodium and potassium salts.
  • a cleaning solution is used in the context of the present invention, which contain a combination of reducing agent and at least one, but especially two or more complexing agents belonging to different classes of substances and optionally a buffer.
  • Said aqueous cleaning 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, emulsified or incorporated as suspended solids.
  • the process according to the invention is carried out in a pH range from about 4.0 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 acceptable salts of weak mineral acids.
  • buffers based on acceptable salts 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
  • an aqueous cleaning solution containing a reducing agent i. in particular dithionite or disulfite or a combination of dithionite and disulfite, and at least one, but especially at least two, complexing agents, i. in particular compounds of the phosphonate and / or succmat type, in the sense of a gentle removal of the iron oxide deposits / deposits of stainless metallic surfaces is improved, when the cleaning solution also carboxylic acids and / or salts thereof are added, such. Oxalic acid and / or salts thereof.
  • carboxylic acids and / or their salts enhances the removal of oxidic iron compounds on the stainless surfaces to be treated, in that these carboxylic acids and / or carbonates can exhibit both complexing and reducing effects.
  • 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 cleaning solution can be prepared before it is brought into contact 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.
  • a two-stage process wherein in a first stage, the reduction stage, a treatment of the surface changes with a reducing agent containing the first cleaning solution I and in a subsequent second stage, a complexing step, a treatment with a second cleaning solution II is carried out, which contains at least one complexing agent which is able to enter into a soluble complex compound with bivalent iron ions.
  • the complexing agent may also be added in situ to cleaning solution I, either directly or with a time lag.
  • the reducing agent and the complexing agent may, as indicated, be added to the cleaning solution in advance or in situ, these in each case in a concentration range of 0.025 wt .-% to 25 wt .-%, in particular in a concentration range of 0.05 wt. % to 15 wt .-%, in particular in a concentration range of 0.1 wt .-% to 10 wt .-%, in particular in a concentration range of 0.2 wt .-% to 5 wt .-%, in particular in a concentration range from 0.25% by weight to 1% by weight, in particular in a concentration range from 0.25% by weight to 0.5% by weight, in particular in a concentration range from 0.5% by weight to 1.5% by weight. % in the cleaning solution.
  • reducing agent and complexing agent in the cleaning solution in a concentration ratio of 6% reducing agent / 10% complexing agent, in particular in a concentration ratio of 5% reducing agent / 8% complexing agent, in particular in a concentration ratio of 3% reducing agent / 5% complexing agent, in particular in a concentration ratio of 1.5% reducing agent / 2.5% complexing agent, in particular in a concentration ratio of 0.6% reducing agent / 1% complexing agent, in particular in a concentration ratio of 0.5% reducing agent / 0.8% complexing agent, in particular in a concentration ratio of 0.3% reducing agent / 0.5% complexing agent, in particular in a concentration ratio of 0.15% reducing agent / 0.25% complexing agent, in particular in a concentration ratio of 0.1% reducing agent / 0.2% complexing agent available.
  • a cleaning solution which comprises a reducing agent such as dithionite or disulfite or a combination of dithionite or disulfite or one of its salts and at least one, but preferably contains at least two complex-forming substances, wherein one of the complex-forming substances is phosphonic acid or one of its salts.
  • Cleaning solutions containing at least two complexing substances are preferably chemically different substances.
  • a cleaning solution which contains dithionite or disulfite or a combination of dithionite or disulfite 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 complexing agent ,
  • the cleaning solution may be composed of dithionite or one of its salts and a combination of phosphonic acid and iminosuccinylic acid, or one of its salts, and optionally a buffer.
  • the cleaning solution may alternatively consist of dithionite or one of its salts and a combination of phosphonic acid and iminosuccinylic 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 phosphonobutane tricarboxylic acid or one of its salts
  • iminosuccinylic acid is an iminodisuccinylic acid or one of its salts.
  • the reducing agent and the complexing agent can be 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% complexing agent before, if the cleaning solution contains only one complexing agent, or in a concentration ratio of 3% reducing agent / 8% complexing agent, in particular 0.5% reducing agent / 1.5% complexing agent, in particular 0.6% reducing agent / 1.1% complexing agent, in particular 0.25% reducing agent / 0.75% complexing agent, in particular in a concentration ratio of 0.3% reducing agent / 0.6% complexing agent, if the cleaning solution two contains different complexing agents.
  • the cleaning solution can 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 having both complexing and reducing properties.
  • the treatment of the deposits and deposits containing oxidic iron compounds on stainless metallic surfaces, in particular on surfaces of stainless steels, is preferably carried out in a temperature range of about 20 ° C to about 98 ° C, in particular in a temperature range of about 40 ° C to about 90 ° C. , in particular in a temperature range of about 50 ° C to about 80 ° C, in particular in a temperature range of about 60 ° C to about 85 ° C, in particular in a temperature range of about 70 ° C to about 80 ° C, and at a pH Value of about 4.0 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 method according to the invention may be designed such that the stainless metallic surfaces, in particular the surfaces of stainless steels, depending on the thickness and extent of the deposits, for a period of about 30 minutes to 12 hours, in particular for a period of 60 minutes to 8 hours, especially 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 with the aqueous cleaning solution in contact.
  • 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 ° 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 is then left at a temperature of 50 ° C. to 95 ° C., in particular from 60 ° C. to 90 ° C., in particular from 70 ° C. to 85 ° C., for a period of 1.0 h to 5 h, in particular 1, 5 hours to 3.0 hours on the surfaces to be cleaned.
  • the cleaning solution can, for example, using the existing in the containers stirring or flow devices or be moved through the system by use of external circulation pumps, with slow flow rates being preferred.
  • the endpoint of a purification 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.
  • iron content measurements e.g., colorimetric
  • the cleaning solution is first removed and the cleaned containers and devices then rinsed with.
  • Repassivation of the stainless steel surfaces can be by means of an aqueous solution containing an oxidizing agent, in particular an oxygen-donating acid (such as HNO 3; ⁇ 20 ppm Cl - or Wasserstoffperxoid) which is able to build up the the stainless steel protective passive layer and optionally at least one complexing agent and / or Use of oxygen-containing ultrapure water, in particular of oxygenated ultrapure water having a conductivity of 0.5 .mu.S / cm and at a temperature of 10 ° C - 20 ° C, in particular from 12 ° C to 15 ° C, preferably at 14 ° C.
  • an oxygen-donating acid such as HNO 3; ⁇ 20 ppm Cl - or Wasserstoffperxoid
  • 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.
  • a purge is carried out using ultrapure water in the sparging process until the conductivity of the effluent water has reached an acceptable level.
  • This value is preferably ⁇ 0.7 ⁇ S / cm.
  • the process can also be carried out so that one places the disassembled parts to be liberated from the coverings / deposits in a bath of a cleaning solution according to the invention.
  • Particularly good cleaning results can also be obtained by the spray process (via, for example, spray balls, C (leaning) I (n) P (lace) sprayers), which is preferably carried out under an inert atmosphere and also forms part 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, produce.
  • Also included in the present invention is a cleaning solution for use in the process of the invention having the composition disclosed hereinbefore.
  • Substances / agents used We use samples of stainless steel tubes (AISI 316L) derived from a pharmaceutical piping system for the distribution of high purity ultrapure water (WFI) and coated with a strong oxidic iron layer (rouging).
  • AISI 316L stainless steel tubes derived from a pharmaceutical piping system for the distribution of high purity ultrapure water (WFI) and coated with a strong oxidic iron layer (rouging).
  • the oxidic iron layer (rouging) is composed in this example chemically predominantly from sparingly soluble Fe (III) compounds.
  • a further improvement of the result can be achieved by adding about 0.5% potassium oxalate to the above-mentioned dithionite solution.
  • reaction solution which contains 15% phosphoric acid and 2% citric acid and has a pH of ⁇ 1 shows no significant change in the surface coating under otherwise identical test conditions (such as reaction time and temperature).
  • the iron content of the solution after 4 h exposure time 0.7 mg / L iron.
  • Substances / agents used Short tube sections of stainless steel tubes (AISI 316L), derived from a pharmaceutical piping system for the distribution of high purity ultrapure water (WFI), are treated with a strong oxidic iron layer (rouging).
  • AISI 316L stainless steel tubes
  • WFI high purity ultrapure water
  • the oxidic iron layer is composed in this example chemically predominantly from sparingly soluble Fe (III) compounds.
  • PBTC-Na4 2-phosphonobutane 1,2,4-tricarboxylic acid sodium salt
  • 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). This layer is abradable with a white wipe and discolored after wiping the top coat red.
  • AISI 316L stainless steel batch tank
  • the oxidic iron layer is composed in this example chemically predominantly from sparingly soluble Fe (III) compounds.
  • Procedure To remove the rouging from the container surface, add a freshly prepared 0.25% solution of solid sodium dithionite in water, the additionally contains 0.5% 2-phosphonobutane 1,2,4-tricarboxylic acid sodium salt (PBTC-Na4), 0.25% tetrasodiumiminodisuccinate, 0.05% potassium oxalate and 0.1% of a sodium bicarbonate / carbonic acid buffer.
  • PBTC-Na4 2-phosphonobutane 1,2,4-tricarboxylic acid sodium salt
  • tetrasodiumiminodisuccinate 0.05% potassium oxalate
  • 0.1% of a sodium bicarbonate / carbonic acid buffer 0.1%
  • Experimental procedure The batch tank is completely filled with 300 liters of the above dithionite solution. The solution (pH (initial) about 7.5) is allowed to act at 75 ° C
  • 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 batching tank (AISI 316L) with CIP spraying equipment used in pharmaceutical production and coated with an oxide iron layer (rouging) is used. This layer is abradable with a white wipe and discolored after wiping the top coat red.
  • AISI 316L stainless steel batching tank
  • rouging oxide iron layer
  • the oxidic iron layer (rouging) is composed in this example chemically predominantly from sparingly soluble Fe (III) compounds.
  • 7.5 is circulated through the circulation pump and piping at 75 ° C for 45 minutes.
  • the vessel wall is permanently wetted with the dithionite solution via the CIP spray ball.
  • the batch tank remains inertized with nitrogen.
  • 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.

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  • Metallurgy (AREA)
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  • 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)
  • Cleaning By Liquid Or Steam (AREA)
  • Detergent Compositions (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (11)

  1. Utilisation d'une solution aqueuse de nettoyage, contenant 0.25 % en poids à 25 % en poids d'un agent réducteur et un ou plusieurs agents complexants en une quantité de 0.2 % en poids à 25 % en poids contenant un acide phosphonique ou un sel de celui-ci pour l'élimination totale de couches de rouging d'une épaisseur de couche comprise entre 0.1 µm et 10 µm sur des surfaces en aciers inoxydables, sélectionnés parmi le groupe des aciers au chrome/nickel et au chrome/nickel/molybdène, en contact avec des fluides dans la plage de pH neutre, dont lesdites surfaces en contact avec des fluides étant des surfaces qui sont exposées à de l'eau ultrapure et/ou à de la vapeur (d'eau) ultrapure, et dont la solution de nettoyage contient une substance supplémentaire qui présente aussi bien des propriétés complexantes que réductrices.
  2. Utilisation selon la revendication 1, caractérisée en ce que lesdits aciers inoxydables sont des aciers inoxydables des degrés de qualité 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) et AISI 904L (1.45339) [*1.xxxx = selon DIN 10027-2].
  3. Utilisation selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que lesdits aciers inoxydables sont des aciers laminés à froid, meulés, décapés ou polis électrolytique, ayant une rugosité de surface Ra < 3.0 µm.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que ladite solution de nettoyage contient au moins 2 agents complexants différents.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que ledit agent réducteur est un dithionite ou un disulfite.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'un acide ρhosphonique choisi dans le groupe des acides hydroxyalcanoïques et alkylènephosphoniques ou un acide 2-phosphonobutane-1.2,4-tricarboxylique ou un de leurs sels est utilisé en tant qu'agent complexant.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'agent réducteur et l'agent complexant sont chacun présents dans la solution de traitement dans une plage de concentration allant de 0.25 % en poids à 10 % en poids
  8. Solution aqueuse de nettoyage contenant 0,25 % en poids à 25 % en poids d'un agent réducteur et un ou plusieurs agents complexants en une quantité de 0.2 % en poids à 25 % en poids contenant un acide phosphonique ou un sel de celui-ci pour l'élimination de couches de rouging d'une épaisseur de couche comprise entre 0 1 µm et 10 µm sur des surfaces en aciers inoxydables, sélectionnés parmi le groupe des aciers au chrome/nickel et au chrome/nickel/molybdène, en contact avec des fluides dans la plage de pH neutre, dont la solution de nettoyage contient une substance supplémentaire qui présente aussi bien des propriétés complexantes que réductrices.
  9. Solution aqueuse de nettoyage selon la revendication 8, caractérisée en ce qu'elle contient au moins deux agents complexants différents.
  10. Solution de nettoyage selon l'une quelconque des revendications 8 ou 9, caractérisée en ce qu'elle contient un dithionite ou un disulfite ou un de leurs sels en tant qu'agent réducteur inorganique, ainsi qu'éventuellement également de l'acide oxalique.
  11. Solution de nettoyage selon l'une quelconque des revendications 8 à 10, caractérisée en ce qu'un acide phosphonique choisi dans le groupe des acides hydroxyalcanoïques et alkylènephosphoniques ou un acide 2-phosphonobutane-1,2,4-tncarboxylique ou un de leurs sels est utilisé en tant qu'agent complexant.
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)

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EP08150974A EP2090676A1 (fr) 2008-02-01 2008-02-01 Procédé destiné l'enlèvement de couches et de dépôts
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
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

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CH699016B1 (de) 2010-10-29
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WO2009095475A1 (fr) 2009-08-06
ATE521732T1 (de) 2011-09-15

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