EP2231843B1 - Verwendung von alkanschwefelsäure zur rostentfernung - Google Patents

Verwendung von alkanschwefelsäure zur rostentfernung Download PDF

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Publication number
EP2231843B1
EP2231843B1 EP09797108.9A EP09797108A EP2231843B1 EP 2231843 B1 EP2231843 B1 EP 2231843B1 EP 09797108 A EP09797108 A EP 09797108A EP 2231843 B1 EP2231843 B1 EP 2231843B1
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Prior art keywords
acid
rust
formulation
organic
weight
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English (en)
French (fr)
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EP2231843A1 (de
Inventor
Jean-Alex Laffitte
Bernard Monguillon
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Arkema France SA
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Arkema France SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • 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
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids

Definitions

  • the present invention relates to the field of cleaning rust on all types of surfaces, including metal surfaces, in particular iron, steel and others. More particularly, the invention relates to the use of alkane sulfonic acid to eliminate rust and rust stains on all types of surfaces, metal or not, and in particular the rust present on metal plates, cables, tubes, pipes , bars, beams and others.
  • the invention also relates to a process for removing rust or rust stains present on said surfaces, in particular metal surfaces, in other words a method for cleaning or releasing surfaces covered wholly or partially by rust .
  • Iron, and more particularly steel is today widely used in many industries, in the form of cables especially for construction, electrical cables, in the form of plates, tubes, masts, bolts, nuts, nails , springs, in the construction industry (bars, beams and beams, and others), transport (automobiles, trains, airplanes, boats, etc.), or in the form of tubes, pipes, and others for the transport fluids, such as liquids (water, sewage, rainwater, sewage, oil) or gas (natural gas among others), packaging (drums, cans, boxes, and others), utensils, tools, metal furniture.
  • transport fluids such as liquids (water, sewage, rainwater, sewage, oil) or gas (natural gas among others)
  • packaging drums, cans, boxes, and others
  • utensils tools, metal furniture.
  • Rust formed on the surface of metals can also be deposited by contact on other non-metallic surfaces, thus causing undesirable rust stains on these non-metallic surfaces.
  • sulphamic acid the releases of which are also considered harmful to the environment, in particular for aquatic organisms, is not an acid that can be widely used industrially to eliminate rust.
  • Nitric acid is also used to eliminate rust from metals.
  • nitric acid in addition to its strong "acid" power, nitric acid is a powerful oxidant, and is therefore very rarely used in large quantities, especially for obvious reasons of user safety.
  • nitric acid is classified as toxic in the Federal Caustic Poison Act, even in diluted form, for all solutions at concentrations greater than 5%.
  • Hydrochloric acid also called muriatic acid
  • vapors and fumes are irritating and toxic to the user.
  • organic acids such as, for example, acetic, citric, oxalic, glycolic, lactic, formic acids, etc.
  • their acidity is lower than the aforementioned mineral acids, their effectiveness is lower, often unsatisfactory and requires the use of larger quantities of products.
  • some are classified as harmful as oxalic and glycolic acid.
  • a first object of the present invention is to provide an effective alternative to the use of the above-mentioned acids, especially phosphoric acid, hydrochloric acid, nitric acid to eliminate rust, especially rust present on all types of surfaces, in particular on metal surfaces, of any type of articles, such as metal plates, cables, tubes, pipes, and others.
  • Another object of the present invention is to provide an effective alternative to acids commonly used in this application while avoiding discharges and effluents harmful to the environment.
  • the formulations based on at least one alkane-sulphonic acid have, in particular, an improved efficiency compared with the phosphoric acid normally used for the removal of rust.
  • alkane-sulfonic acid s
  • s alkane-sulfonic acid
  • the use according to the invention provides an effective alternative and complies with the environmental rules to the use of phosphoric acid usually used in these conditions.
  • the present invention provides a phosphoric acid replacement product for cleaning metal surfaces, in particular for the removal of rust, said substitute being biodegradable, less toxic to the environment, more efficient and can be used in smaller quantities, while ensuring comparable or even higher efficiency.
  • rust means the product of corrosion by oxygen and water, iron and iron-containing metals, especially steels. These corrosion products are in particular the oxides and hydroxides of iron (II), the oxides and hydroxides of iron (III), optionally in the form of hydrates, and for example Fe 2 O 3 , FeO (OH), Fe (OH ) 3 , Fe 2 O 3 , ⁇ n H 2 O.
  • alkanesulphonic acid means the alkanesulphonic acids of formula R-SO 3 H, where R represents a linear or branched saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms.
  • alkane-sulphonic acids that can be used in the context of the present invention are preferably chosen from methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid and iso- propanesulfonic acid. n-butanesulfonic acid, iso- butanesulfonic acid, sec- butanesulfonic acid, tert -butanesulphonic acid, and mixtures of two or more of them in all proportions.
  • the alkane-sulphonic acid used in the context of the present invention is methanesulfonic acid or ethanesulphonic acid, and the acid used is preferably the acid. methanesulfonic.
  • the use according to the present invention uses at least one alkane-sulphonic acid chosen from linear or branched chain alkane sulphonic acids containing from 1 to 4 carbon atoms, and preferably at least methane acid.
  • alkane-sulphonic acid chosen from linear or branched chain alkane sulphonic acids containing from 1 to 4 carbon atoms, and preferably at least methane acid.
  • AMS sulfonic
  • any type of formulation comprising at least one alkanesulfonic acid may be suitable, the alkane-sulfonic acid (s) may be used in pure form or in diluted form using various components, such as indicated below.
  • the formulation comprises from 0.01% to 90% by weight of alkane-sulphonic acid (s), in particular from 0.5% to 75% by weight, relative to the total weight of said formulation.
  • the concentration of alkane-sulfonic acid (s) in the formulation depends on many factors, among which are the amount of rust or rust stains to be cleaned, the nature and shape of the surface to be cleaned, the temperature at which the formulation is applied, and others. Those skilled in the art will be able to adapt the concentration of acid in the formulation without excessive efforts.
  • Concentrated solutions for example from 60% to 100%, preferably from 70% to 100% by weight of alkane-sulphonic acid, relative to the total weight of said formulation, are preferred when it is desired to remove significant amounts.
  • rust especially on the surface of metals, or on the surface of materials that are not very sensitive to acid attack.
  • Less concentrated solutions of 0.01% to 60%, preferably 0.05% to 50% are preferred for lower amounts of rust to be removed, or for cleaning rust stains on surfaces, especially non-metallic surfaces. , sensitive to acid attacks.
  • the formulation is for example an aqueous, organic, or even hydro-organic formulation, which can be prepared as a concentrated, concentrated mixture which can be diluted by the end user.
  • the formulation may also be a ready-to-use formulation, i.e., it does not need to be diluted.
  • methane sulfonic acid in aqueous solution sold by Arkema under the name Scaleva ®, or under the name Lutropur ® marketed by BASF, ready for use or diluted with water in the proportions indicated above.
  • the formulation used in the present invention comprises one or more additives, as indicated above.
  • the formulation is a formulation in the form of a gel. It has indeed been observed that formulations in the form of alkane-sulphonic acid gel (s) are very effective for the removal of rust, not only because of the gel itself which allows a longer action acid active principle (the gel "adheres" longer on the surfaces, compared to an aqueous formulation), but also has an improved cleaning power, compared to other formulations-gels, for example formulations in the form of gel phosphoric acid.
  • s alkane-sulphonic acid gel
  • the gelling agents and the surfactants that can be used in the formulations in the form of a gel can be of any type.
  • the person skilled in the art will know, without particular difficulty and drawing inspiration from the examples which follow, to choose and adapt the nature of the gelling agents and the appropriate surfactants.
  • the present invention relates to the use of a foaming gel formulation.
  • Foaming gels are indeed particularly interesting because they produce a sticky foam, that is to say an adherent foam, rusty surfaces, while requiring a lower consumption of active ingredient cleaning acid, and have the advantage better rinsability, that is to say a simpler and more efficient disposal, while requiring a smaller amount of water.
  • the formulation may be prepared in the form of a concentrate, and with a suitable viscosity, and then diluted before use until the expected efficiency, viscosity and foaming power.
  • At least one ethoxylated amine oxide such as, without limitation, Cecajel ® OX100 from CECA, or Aromox ® T12 from Akzo alone or combination with at least one dimethylalkylamine oxide allows to bring stability to the foaming gel.
  • Foaming agents and in particular those described above, generally form gels when they are mixed with water, that is to say they increase the viscosity of the formulation, without it being necessary. to add a gelling agent.
  • a gelling agent generally form gels when they are mixed with water, that is to say they increase the viscosity of the formulation, without it being necessary.
  • the addition of such a gelling agent is not excluded from the present invention.
  • solubilizing or hydrotropic agents that may be used in the formulations according to the invention, mention may be made, for example and without limitation, of sodium xylene or cumene sulfonates. Such agents are however not essential in the acidic formulations according to the invention.
  • An aqueous, organic or hydro-organic formulation in the form of a solution, a gel or in the form of a foaming gel, which is particularly preferred, is a formulation comprising from 0.01% to 97%, preferably from 0.05% to 75% more preferably from 0.5% to 70% by weight of methanesulfonic acid.
  • formulations used according to the present invention may be applied according to any method known to those skilled in the art, and in particular under pressure, or using a spray gun.
  • the present invention relates to a rust removal method, for example in the form of a layer (s) or simply a stain (s) comprising at least one step of contacting an effective amount of a clear formulation as defined above, with the rust to be eliminated, by contact, immersion, spraying, spraying, application of a more or less thick layer, possibly using appropriate tools known to those skilled in the art (brushes , brushes, spatulas, and others), said contacting step possibly being followed by one or more rinsing and / or drying steps.
  • a rust removal method for example in the form of a layer (s) or simply a stain (s) comprising at least one step of contacting an effective amount of a clear formulation as defined above, with the rust to be eliminated, by contact, immersion, spraying, spraying, application of a more or less thick layer, possibly using appropriate tools known to those skilled in the art (brushes , brushes, spatulas, and others), said contacting step possibly being followed by one or more rin
  • the temperature at which the process is carried out can vary in large proportions and is generally between -20 ° C and + 150 ° C, preferably between 0 ° C and 80 ° C, more preferably between 10 ° C and 80 ° vs.
  • the use temperature is the ambient temperature or a temperature between room temperature and about 80 ° C. It can thus be envisaged to heat the alkane-sulfonic acid and the surface to be treated, this temperature may be identical or different, or to bring to temperature either the alkane-sulfonic acid or the surface to be treated.
  • the cleaned surface may be, the case sinning and if necessary, dried, according to any method known to those skilled in the art, by example in air, under a current of air more or less hot, in an oven, by heating (electric, heat lamps), wiping (paper or absorbent textiles), and others.
  • the alkanesulfonic acid is advantageously used in the form of a formulation, for example an aqueous, organic or hydro-organic formulation, in liquid form, of a gel or of a foaming gel, as defined above.
  • effective amount means an amount for the dissolution of rust and removal of any traces of rust.
  • This amount can vary in large proportions, depending on the surfaces to be treated and the amount of rust, the temperature and pressure of the formulation used, the desired duration of the removal process, and others.
  • the amount of acid will be advantageously established to allow complete elimination of rust, while observing a minimum amount of acid (s), mainly for economic reasons.
  • the rust removal process may be repeated one or more times depending on the amount of rust to be removed, and its degree of encrustation.
  • reaction time necessary for the dissolution of the rust, rust spots
  • this reaction time may vary from a few seconds to a few hours, or even a few days, depending on the temperature at which the cleaning is carried out, the application pressure of the alkane-sulphonic acid (s), the amount of rust to be removed, its degree of encrustation, and than the nature of the surface to be treated.
  • the treatment with at least one alkane-sulphonic acid as just defined may optionally be accompanied and / or followed by one or more mechanical operations (stirring, scraping, brushing, and the like), in order to improve acidic chemical action, if necessary.
  • the treatment may be followed by one or more rinsing operations, for example with clear water, solvent (s) or mixture (s) water / solvent (s).
  • Alkanesulphonic acids especially methanesulfonic acid
  • methanesulfonic acid have been found to be more effective than phosphoric acid in the removal of rust, and rust stains, which allows for the use of lower amounts of acids and more environmentally friendly: the effluents (residues, salts and others) resulting from cleaning with at least one alkanesulphonic acid are biodegradable, unlike the phosphoric acid commonly used today which generates phosphates, responsible among other things eutrophication phenomena of rivers, streams, and water reserves, such as lakes, marshes, groundwater, etc.
  • alkane-sulphonic acids used in the present invention have, compared to aryl-sulphonic acids, the advantage of generating a lower oxygen demand at the effluent treatment stations (chemical oxygen demand, COD). and consequently allow a higher concentration of organic discharges in said stations.
  • the present invention described above shows that it is possible to eliminate rust on all types of surfaces, to clean rust stains present on all types of surfaces, whether metallic or non-metallic, such as polymers, textiles, wood, and others.
  • the surfaces are selected from metals (iron, steel, copper, alloys, and others), polymers (plastics, paints, varnishes, lacquers, etc.), concretes, cements, tiles, porcelains , wood, paper, cardboard, textiles, glasses, and others.
  • the alkane-sulphonic acids can advantageously be used as a replacement for the acids commonly used, for the elimination of rust and rust stains in a large number of fields of application among which may be mentioned in a non-limiting manner the fields of construction (plates, bolts, nuts, screws, nails, springs, bars, beams, beams, and others), cable, for example electrical wiring, transportation (automobiles, trains, airplanes, boats, etc.), transportation of fluids, such as water, wastewater, rainwater, sewage, oil, or gas, natural gas among others (tubes, pipes, and others), packaging (drums, cans, boxes, and others), utensils, tools, metal furniture, to name a few of them.
  • fields of construction plates, bolts, nuts, screws, nails, springs, bars, beams, beams, and others
  • cable for example electrical wiring
  • transportation autonomousmobiles, trains, airplanes, boats, etc.
  • transportation of fluids such as water, wastewater, rainwater, sewage, oil, or gas, natural gas
  • the alkane sulphonic acids used in the context of the present invention may prove effective for cleaning copper electrical cables soiled with various metal oxides, and in particular copper oxides, or for eliminating organic soiling (excrements). and animal droppings), tartar, and others.
  • the bottle is closed with a stopper and then placed in a stirred bath for 24 hours at 70 ° C.
  • the solution is then cooled and filtered on a membrane filter (Acrodisc ® 25 mm diameter and 0.2 ⁇ m porosity).
  • the filtrate is assayed by ICP (emission spectroscopy) to evaluate the iron content in the filtrate. The higher the iron content in the filtrate, the better the effectiveness of the acid for rust removal.
  • methanesulfonic acid has an efficiency greater than that of phosphoric acid and in particular up to 17 times higher for concentrations at 10% by weight in water.
  • the nail After rinsing with clean water, the nail no longer contains any rust.

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

Claims (9)

  1. Verwendung einer wässrigen, organischen oder wässrig-organischen Formulierung zur Entfernung von Rost, bestehend aus mindestens einer Alkansulfonsäure der Formel R-SO3H, wobei R für eine gesättigte, lineare oder verzweigte Kohlenwasserstoffkette mit 1 bis 4 Kohlenstoffatomen steht, gegebenenfalls in Kombination mit einem oder mehreren Additiven, ausgewählt aus:
    • Lösungsmitteln, hydrotropen Mitteln oder Lösungsvermittlern oder Gelbildnern,
    • Bioziden, Desinfektionsmitteln,
    • Rheologie- oder Textur- oder Verdickungsmitteln,
    • organischen oder anorganischen Säuren,
    • Flammschutzmitteln,
    • Konservierungsstoffen,
    • anionischen, kationischen, nichtionischen oder amphoteren Tensiden, Emulgatoren, Detergentien, Seifen,
    • Schaummitteln, Antischaummitteln,
    • Frostschutzmitteln,
    • Farbmitteln,
    • Duftstoffen, Geruchsmitteln.
  2. Verwendung nach Anspruch 1, wobei die Alkansulfonsäure aus Methansulfonsäure, Ethansulfonsäure, n-Propansulfonsäure, Isopropansulfonsäure, n-Butansulfonsäure, Isobutansulfonsäure, sec-Butansulfonsäure, tert-Butansulfonsäure und Mischungen von zwei oder mehr davon in allen Anteilen ausgewählt ist.
  3. Verwendung nach Anspruch 1 oder Anspruch 2, wobei es sich bei der Alkansulfonsäure um Methansulfonsäure oder Ethansulfonsäure, vorzugsweise Methansulfonsäure, handelt.
  4. Verwendung nach einem der vorhergehenden Ansprüche, wobei die Konzentration an Alkansulfonsäure(n) zwischen 0,01 und 90 Gew.-%, insbesondere zwischen 0,5 und 75 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, liegt.
  5. Verwendung nach einem der vorhergehenden Ansprüche, wobei mindestens eine Alkansulfonsäure in einer konzentrierten, gebrauchsfertigen oder vor der Verwendung zu verdünnenden wässrigen, organischen oder wässrig-organischen Formulierung vorliegt.
  6. Verwendung nach einem der vorhergehenden Ansprüche, wobei mindestens eine Alkansulfonsäure in einer Flüssig-, Gel- oder Schaumgelformulierung verwendet wird.
  7. Verfahren zur Entfernung von Rost, umfassend mindestens einen Schritt des Inberührungbringens einer wirksamen Menge einer Formulierung nach einem der vorhergehenden Ansprüche mit dem zu entfernenden Rost durch Kontakt, Eintauchen, Besprengen, Besprühen, Aufbringen einer mehr oder weniger dicken Schicht, wobei auf den Schritt des Inberührungbringens gegebenenfalls ein oder mehrere Spül- und/oder Trocknungsschritte folgen.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass es bei einer Temperatur zwischen -20°C und +150°C, vorzugsweise zwischen 0°C und 80°C, noch weiter bevorzugt zwischen 10°C und 80°C, vorzugsweise bei Umgebungstemperatur oder auch bei einer Temperatur zwischen Umgebungstemperatur und ungefähr 80°C, durchgeführt wird.
  9. Verwendung nach einem der Ansprüche 1 bis 6 zum Abreinigen von Rost auf allen Arten von metallischen oder nichtmetallischen Oberflächen und insbesondere auf Metallen, Betonen, Zementen, Fliesen, Porzellan, Holz, Papier, Pappe, Textilien, Kunststoffen, Gläsern.
EP09797108.9A 2008-11-28 2009-11-27 Verwendung von alkanschwefelsäure zur rostentfernung Active EP2231843B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0858129A FR2939146B1 (fr) 2008-11-28 2008-11-28 Utilisation d'acide alcane sulfonique pour elimination de la rouille
PCT/FR2009/052321 WO2010061146A1 (fr) 2008-11-28 2009-11-27 Utilisation d'acide alcane sulfonique pour elimination de la rouille

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Publication Number Publication Date
EP2231843A1 EP2231843A1 (de) 2010-09-29
EP2231843B1 true EP2231843B1 (de) 2015-07-22

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US (1) US8574370B2 (de)
EP (1) EP2231843B1 (de)
CA (1) CA2711205C (de)
ES (1) ES2545608T3 (de)
FR (1) FR2939146B1 (de)
WO (1) WO2010061146A1 (de)

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DE102016107681A1 (de) * 2016-04-26 2017-10-26 Kerona Gmbh Substanz zum Lösen von Korrosionsschichten
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CN113696064B (zh) * 2021-09-06 2023-01-03 贝林集团有限公司 一种绿色建筑用金属表面除锈喷涂设备

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US8574370B2 (en) 2013-11-05
FR2939146A1 (fr) 2010-06-04
ES2545608T3 (es) 2015-09-14
US20110214690A1 (en) 2011-09-08
EP2231843A1 (de) 2010-09-29

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