EP2231843A1 - Verwendung von alkanschwefelsäure zur rostentfernung - Google Patents

Verwendung von alkanschwefelsäure zur rostentfernung

Info

Publication number
EP2231843A1
EP2231843A1 EP09797108A EP09797108A EP2231843A1 EP 2231843 A1 EP2231843 A1 EP 2231843A1 EP 09797108 A EP09797108 A EP 09797108A EP 09797108 A EP09797108 A EP 09797108A EP 2231843 A1 EP2231843 A1 EP 2231843A1
Authority
EP
European Patent Office
Prior art keywords
acid
rust
use according
alkane
formulation
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
EP09797108A
Other languages
English (en)
French (fr)
Other versions
EP2231843B1 (de
Inventor
Jean-Alex Laffitte
Bernard Monguillon
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.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2231843A1 publication Critical patent/EP2231843A1/de
Application granted granted Critical
Publication of EP2231843B1 publication Critical patent/EP2231843B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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, particularly 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 spots present on said surfaces, in particular metal, in other words a cleaning process or bare exposed surfaces covered in whole or in part 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, poles, 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 of fluids, such as liquids (water, sewage, rainwater, sewage, oil) or gas (natural gas among others), packaging (drums, cans, boxes, and others), utensils, tools, furniture metallic.
  • Nitric acid is also used to eliminate rust from metals.
  • 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
  • rust a substance that causes rust.
  • vapors and clear are irritating and toxic to the user.
  • organic acids such as, for example, acetic acid, citric acid, oxalic acid, glycolic acid, lactic acid, formic acid, etc.
  • a first object of the present invention is to provide an effective alternative to the use of the aforementioned acids, including phosphoric acid, hydrochloric, nitric to eliminate rust, including rust on all types of surfaces , especially 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 invention relates to the use of at least one alkane-sulfonic acid for the removal of rust which may be present on any type of surface, especially metal, and particularly on plate surfaces, cables, tubes, pipes, and others.
  • the use according to the invention provides an effective alternative and complies with environmental rules for 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 replacement product being biodegradable, less toxic to the environment, more efficient and can be used in smaller quantities, while ensuring comparable or even higher efficiency.
  • alkane-sulphonic acid is understood to mean alkanesulfonic acids of formula R-SO 3 H, where R represents a saturated hydrocarbon-based chain, linear or branched, having from 1 to 4 carbon atoms.
  • the alkane-sulphonic acids that can be used in the context of the present invention are preferably chosen from methanesulfonic acid, ethanesulfonic acid, n-propane-sulphonic acid and / or acid. propanesulphonic acid, n-butanesulfonic acid, n-butanesulfonic acid, sec-butanesulphonic acid, tert-butanesulphonic acid, and mixtures of two or more of between 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 methanesulfonic acid.
  • the use according to the present invention implements at least one alkane-sulphonic acid chosen from linear or branched chain alkane-sulphonic acids containing from 1 to 4 carbon atoms, and preferably from at least 1 carbon atoms.
  • alkane-sulphonic acid chosen from linear or branched chain alkane-sulphonic acids containing from 1 to 4 carbon atoms, and preferably from at least 1 carbon atoms.
  • any type of formulation comprising at least one alkane-sulfonic acid may be suitable, the alkane-sulfonic acid (s) may be used in pure form or in diluted form using various components, as indicated below.
  • the formulation comprises from 0.01% to 100% by weight of alkanesulfonic acid, more usually from 0.05% to 90% by weight, in particular from 0.5% to 75% by weight of alkanesulfonic acid, based on the total weight of said formulation.
  • the concentration of alkane-sulfonic acid (s) in the formulation depends on many factors, among which mention may be made of the amount of rust or rust stains to be cleaned, the nature and shape of the surface to be cleaned. clean, 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 are preferred, for example from 60% to 100%, preferably from approximately 70% to 100% by weight of alkanesulfonic acid, relative to the total weight of said formulation, when it is desired to remove large amounts of 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 formulation, organic, or hydro-organic, which can be prepared as a concentrated, concentrated mixture that 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.
  • a ready-to-use formulation i.e., it does not need to be diluted.
  • methanesulfonic acid in aqueous solution sold by Arkema under the name Scaleva ®, or under the name Lutropur ® marketed by BASF, ready for use or diluted water in the proportions indicated above.
  • the formulation used in the present invention may optionally comprise one or more additives, such as those chosen from: • solvents, hydrotropic or solubilizing agents (for example alcohols, esters, ketones, amides , and others), • biocides, disinfectants (bromoacetic acid, peracetic acid, hydrogen peroxide, and others),
  • solvents for example alcohols, esters, ketones, amides , and others
  • biocides for example alcohols, esters, ketones, amides , and others
  • disinfectants bromoacetic acid, peracetic acid, hydrogen peroxide, and others
  • rheological or texturizing agents or thickeners or gelling agents sucrose, polysaccharides, alginates, silica, amorphous silica, gums and others
  • organic or inorganic acids eg sulfuric, phosphoric, nitric, sulphamic, acetic, citric, formic, lactic glycolic, oxalic and other
  • Anionic, cationic, nonionic or amphoteric surfactants such as ethoxylated alcohols and / or amines, alkyl and / or aryl sulfonates), emulsifiers, detergents, soaps, and the like;
  • Anti-gels for example ethylene glycol, propylene glycol, and others
  • the formulation is a formulation in the form of a gel. It has indeed been observed that the formulations in the form of alkane-sulfonic 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.
  • the present invention relates to the use of a formulation in gel form comprising:
  • 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 formulation in the form of a foaming gel.
  • 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 cleaning acid active ingredient, and have the advantage of better rinsability, that is to say a simpler and more efficient disposal, while requiring a smaller amount of water.
  • the present invention relates to the use of a formulation in the form of a foaming gel comprising: from 0.01% to 97% by weight, preferably from 0.05% to 75% by weight and more particularly from 0.5% to 70% by weight of at least one alkanesulfonic acid, preferably methanesulfonic acid;
  • At least one additive chosen from those mentioned above, preferably from 0 to 10% by weight, preferably from 0.1 to 5% by weight, of a solubilizing or hydrotropic agent, and 0 to 20% by weight, preferably 0.5 to 10% by weight, of at least one surfactant;
  • 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 is obtained, as regards viscosity and foaming power.
  • the foaming agent may be chosen from foaming agents commonly used by those skilled in the art, and preferably from amine oxides, such as for example:
  • Dimethylalkylamine oxides the alkyl chain being a "fatty" chain, containing, for example, from 10 to 30 carbon atoms, preferably from 12 to 22 carbon atoms,
  • At least one ethoxylated amine oxide such as, but not limited to, Cecajel ® OX100 from CECA, or Aromox ® T12 from Akzo alone or combination with at least one Dimethylalkylamine oxide provides stability to the foaming gel.
  • the foaming agents and in particular those described above, generally form gels when they are mixed with water, that is to say that they increase the viscosity of the formulation, without which it is necessary to add a gelling agent.
  • a gelling agent is not excluded from the present invention.
  • solubilizing or hydrotropic agents that can be used in the formulations according to the invention, mention may be made, by way of example and in a nonlimiting manner, 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 of 0.05%. at 75%, more preferably from 0.5% to 70% by weight of methanesulfonic acid.
  • the formulations used according to the present invention whether in liquid form, gels or foaming gels, concentrated or diluted, can 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 process, for example in the form of layer (s) or simply stain (s) comprising at least one step of contacting a quantity effective of at least one alkanesulfonic acid, as defined above, preferably the acid methanesulfonic, 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 the like), said contacting step possibly being followed by one or more rinsing and / or drying steps.
  • a rust removal process for example in the form of layer (s) or simply stain (s) comprising at least one step of contacting a quantity effective of at least one alkanesulfonic acid, as defined above, preferably the acid methanesulfonic, 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
  • the temperature at which the process is carried out may 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 ° C.
  • the use temperature is the ambient temperature or else a temperature between room temperature and approximately 80 ° C. It can thus be envisaged to heat the alkanesulfonic acid and the surface to be heated. treat, this temperature may be the same or different, or to bring temperature is the alkanesulfonic acid or the surface to be treated.
  • the cleaned surface can be, if necessary and if necessary, dried, according to any known method of the man of the occupation, for 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, as a gel or as 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 total elimination of rust, while observing a minimum amount of acid (s), mainly for economic reasons.
  • the rust removal process can be repeated one or more times depending on the amount of rust to eliminate, and its degree of incrustation.
  • the contacting of an effective amount of at least one alkanesulfonic acid is followed by a 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-sulfonic acid (s), the amount of rust to be removed, its degree of incrustation , as well as 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 to improve the 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).
  • the alkane-sulfonic acids especially methanesulfonic acid, have proved more effective than phosphoric acid in the elimination of rust, and rust spots, which allows the use of amounts of Less acid and more environmentally friendly: the effluents (residues, salts and others) resulting from cleaning with at least one alkane-sulfonic 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.
  • the 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, clean rust spots on all types of surfaces, whether metallic or non-metallic, such as 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-sulfonic acids can advantageously be used as a replacement for commonly used acids, for the removal of rust and rust stains in a large number of fields of application among which may be mentioned in a non-limiting manner.
  • the use according to the present invention allows not only the cleaning of the rust, but also concomitantly, cleaning other (s) type (s) of dirt (s) may be present on the surfaces to be treated, because of the acidic nature of the alkane-sulphonic acids used.
  • the alkane sulfonic acids used in the context of the present invention can be effective for cleaning copper electrical cables soiled with various metal oxides, and in particular copper oxides, or to remove dirt. organic (droppings and animal droppings), tartar, and others.
  • Fe 2 O 3 ferric oxide dissolution tests were carried out in powder form (5 ⁇ m, purity). > 99%), according to the following protocol: [0067] in a bottle were added 6 g of iron oxide and 100 g of an aqueous solution of methanesulfonic acid (Scaleva ® marketed by Arkema) at various concentrations . In parallel, comparative tests are carried out with 100 g of an aqueous solution of phosphoric acid (Normapur, marketed by VWR), at the same various concentrations. The bottle is closed by a stopper, then placed in a stirred bath during
  • the 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 clear water, the nail no longer contains any trace of 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)
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

Publications (2)

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

Family

ID=40763992

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09797108.9A Active EP2231843B1 (de) 2008-11-28 2009-11-27 Verwendung von alkanschwefelsäure zur rostentfernung

Country Status (6)

Country Link
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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Publication number Priority date Publication date Assignee Title
DE102013217325A1 (de) * 2013-08-30 2015-03-05 Werner & Mertz Gmbh Reinigungsmittel mit Entkalkungswirkung
CN104088463B (zh) * 2014-06-24 2016-08-17 福建海源新材料科技有限公司 建筑模板上的水泥清理方法
DE102015117955B4 (de) * 2015-10-21 2019-05-09 Witty Gmbh & Co. Kg Verfahren zur Reinigung und Desinfektion von Trinkwasserbehältern
DE102016107681A1 (de) * 2016-04-26 2017-10-26 Kerona Gmbh Substanz zum Lösen von Korrosionsschichten
CN107418609B (zh) * 2017-06-30 2019-05-03 河南地之绿环保科技有限公司 一种处理裂解炉内表面的方法
FR3079528A1 (fr) * 2018-03-29 2019-10-04 Suez Groupe Procede de prevention de la formation de rouille blanche sur une surface en acier recouverte de zinc
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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Also Published As

Publication number Publication date
ES2545608T3 (es) 2015-09-14
US20110214690A1 (en) 2011-09-08
US8574370B2 (en) 2013-11-05
EP2231843B1 (de) 2015-07-22
CA2711205A1 (fr) 2010-06-03
CA2711205C (fr) 2014-11-04
FR2939146A1 (fr) 2010-06-04
WO2010061146A1 (fr) 2010-06-03
FR2939146B1 (fr) 2012-11-16

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