EP2358924A2 - Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion - Google Patents

Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion

Info

Publication number
EP2358924A2
EP2358924A2 EP09751935A EP09751935A EP2358924A2 EP 2358924 A2 EP2358924 A2 EP 2358924A2 EP 09751935 A EP09751935 A EP 09751935A EP 09751935 A EP09751935 A EP 09751935A EP 2358924 A2 EP2358924 A2 EP 2358924A2
Authority
EP
European Patent Office
Prior art keywords
acid
composition according
composition
independently represent
pickling
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.)
Withdrawn
Application number
EP09751935A
Other languages
German (de)
English (en)
Inventor
Stefan Fassbender
Peter Kolb
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09751935A priority Critical patent/EP2358924A2/fr
Publication of EP2358924A2 publication Critical patent/EP2358924A2/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • 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
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
    • 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
    • C23G1/081—Iron or steel solutions containing H2SO4
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon

Definitions

  • the present invention relates to an acidic aqueous composition containing a thiodiglycol alkoxylate for treating metallic surfaces.
  • the surface of a metal is treated with a treatment solution and thereby chemically altered.
  • surface layers such as corrosion layers and deposits are removed and, if appropriate, protection and effect layers are built up.
  • the main purpose of the treatment is to remove various oxide layers such as rust or scale and / or other contaminants such as fats, oils or lime from the surface and / or to activate and / or protect the surface.
  • An example of a protective treatment is the acid phosphating of an iron or steel surface.
  • the essential element in treating or pickling is an attack on the metal. During phosphating with an acidic zinc phosphate solution, attacking an acid on the metal directly on the metal surface consumes many H + ions, causing the pH value to rise locally. Only then is the solubility product for zinc phosphate exceeded, so that zinc phosphate can be deposited in a thin layer on the surface.
  • aqueous, inorganic or organic acids in particular hydrochloric acid, phosphoric acid or sulfuric acid and, as a rule, auxiliaries, such as surfactants, are used.
  • various metal components such as reactors, pipelines, boilers, heat exchangers and the like can be pickled or chemically cleaned.
  • the components are thereby cleaned of different iron oxides (rust) such as Fe 2 ⁇ 3, Fe 3 ⁇ 4 , FeO and the like and of calcium and magnesium deposits, known as scale.
  • rust iron oxides
  • a small amount of corrosion inhibitor is frequently added to the acid pickling solution, which should prevent or at least greatly slow down the dissolution of the base material, of the metal, by corrosion.
  • alkyne alkoxylates as corrosion inhibitors for strongly acidic mordants. These are described, for example, in WO 2005/033364.
  • JP-A 10-130873 teaches the use of polythiopolyether diols as a corrosion inhibitor.
  • the compounds disclosed in this document contain at least two structural elements of the general formula - (O-RS) -.
  • the preparation of such polythiopolyether diols by means of polycondensation is disclosed in US Pat. No. 2,518,245. there Polymers are obtained which contain several sulfur atoms. These are then used in lubricants.
  • the object of the invention is to provide an acidic, aqueous composition for pickling metallic surfaces which contains a corrosion inhibitor, which is superior to the corrosion inhibitors known from the prior art, especially in strongly acidic media and at high temperatures.
  • a further object of the invention is to provide a process for pickling metallic surfaces, in particular steel surfaces, in which hardly any pitting arises even when using strongly acidic media.
  • an acidic, aqueous composition for pickling metallic surfaces containing one or more acid (s), water and one or more compound (s) of the general formula (I)
  • groups A and B can be randomly distributed, alternating or in the form of two or more blocks in any order,
  • the compound according to the general formula (I) has very good anticorrosive properties when p and p 'each correspond to the number 2.
  • n + m and n '+ m' each independently correspond to an integer from 1 to 50, preferably an integer from 5 to 30, preferably an integer from 18 to 22, most preferably 19 until 21.
  • n and m denote an average value, which is the average for the alkoxylates.
  • ethyleneoxy units and subsequently propyleneoxy units, butyleneoxy units and / or pentyleneoxy units can also be present on the alcohol radicals.
  • statistical mixtures of ethylene oxide units, propyleneoxy units, butyleneoxy units and / or pentyleneoxy units can be present.
  • Three or more block alkoxylation and mixed alkoxylation are also possible. It is also possible that preferably only ethylene oxide units (A) are present.
  • n and n ' are then particularly preferably each independently a number from 1 to 25, m and m' are then each independently preferably a number from 1 to 25.
  • the proportion of ethylene oxide units (A), based on the alkoxylates, in the thio according to the invention is Diglycol ethoxylate according to the general formula (I) 50 mol%, more preferably 70 MoI%, particularly preferably 90 mol%, most preferably 100 mol%.
  • the present invention relates to the use of an encryption Thiodiglykolethoxylats, which is marketed by BASF under the trade name SE Lugalvan ® HS 1000th
  • Lugalvan ® HS 1000 is a Thiodiglykolethoxylat which tion by those skilled known ethoxylation of thiodiglycol with KOH catalysis at a temperature of 130 0 C is established.
  • the potassium hydroxide used is neutralized by addition of acetic acid after completion of the ethoxylation.
  • the illustration is shown schematically below:
  • molecular weight is about 1000 g / mole, and n is about 20.
  • thiodiglycol ethoxylates having a molecular weight of from 500 to 10,000, preferably from 750 to 2,000, particularly preferably from 800 to 1,200 g / mol, have proven to be particularly suitable corrosion inhibitors.
  • the invention further relates to a method for pickling metallic surfaces by treating the metallic surfaces with the acidic, aqueous composition.
  • the inventive method can be used for pickling metallic surfaces of various kinds.
  • the metals may be pure metals as well as alloys. Examples include surfaces of iron, cast iron, steel, nickel, zinc, brass or aluminum, wherein in each case the topmost metal layer which comes into direct contact with the aqueous composition according to the invention is meant.
  • the metallic surface may also be, for example, surface-tempered steels, such as hot or galvanized steels.
  • the method is particularly suitable for pickling surfaces of (cast) iron, stainless steel, steel or aluminum, most preferably for steel surfaces.
  • the method is particularly suitable for pickling the surface of band metals, such as steel or aluminum bands.
  • the metallic surfaces can be both outer surfaces of metallic materials, such as the surface of metallic strips, sheets or else irregularly shaped workpieces such as machine parts. It may also be internal surfaces, such as the internal surfaces of pipelines, heat exchangers, reactors, boilers, chemical plants, petroleum extraction plants or the like.
  • unwanted surface layers and impurities are removed and a protective layer is applied.
  • unwanted surface layers may be inorganic layers, for example largely oxidic layers such as rust layers, scale layers or layers which are formed during pickling of metals, for example steel. They may be applied to temporary corrosion protection layers, such as phosphate layers or layers of other materials, such as carbonate layers such as limestone layers or patina layers.
  • the unwanted layers may also be thin layers of organic materials such as grease or oil layers.
  • the aqueous composition used in the process according to the invention comprises water and one or more acids in a total amount of from 60 to 99.99% by weight.
  • the total amount of water and acid is 60 to 99.99 wt .-% and most preferably 80 to 99.99 wt .-%.
  • the acid may be an inorganic acid such as hydrochloric acid, hypo- and chloric acid, sulfuric acid, amidosulfonic acid, phosphoric acid or phosphorous acid, or an organic acid such as formic acid, methanesulfonic acid, acetic acid, citric acid or succinic acid.
  • an inorganic acid such as hydrochloric acid, hypo- and chloric acid, sulfuric acid, amidosulfonic acid, phosphoric acid or phosphorous acid
  • an organic acid such as formic acid, methanesulfonic acid, acetic acid, citric acid or succinic acid.
  • mixtures of different acids can be used, for example mixtures of hydrochloric acid and phosphoric acid.
  • the acid is preferably sulfuric acid, methanesulfonic acid or phosphoric acid.
  • the composition according to the invention generally comprises at least 50% by weight of water, preferably at least 60% by weight of water.
  • the total amount of water in the composition of the invention is calculated here as the sum of the water, wel This is added together with the acid, and from that which is added in pure form or in the form of solutions of other materials.
  • the compound of the general formula (I) contained in the composition according to the invention is, according to a general embodiment, in an amount of 0.01 to 2 wt .-%, preferably in an amount of 0.05 to 2 wt .-%, particularly preferably in an amount of 0.1 to 1 wt .-% in the inventive composition.
  • All concentration data refer to the ready-to-use composition. It is of course possible first to produce a concentrate, which is first diluted to the desired concentration on site.
  • composition of the invention used in the process generally further comprises one or more additives or auxiliaries, even if their addition is not absolutely mandatory in every case.
  • the amount of such additives is 0 to 38 wt .-%, preferably 0.01 to 30 wt .-% and particularly preferably 0.1 to 20% by weight.
  • Excipients are in particular from 0.01% by weight to 20% by weight of at least one surface-active substance. Preferably, 0.1 to 10 wt .-% and particularly preferably 0.5 to 8 wt .-% of the surfactant used.
  • suitable surfactants include conventional anionic, cationic or nonionic surfactants.
  • Suitable nonionic surfactants are, in particular:
  • Alkoxylated C 8 -C 22 -alcohols such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates:
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
  • Preferred alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • Alkylphenol alkoxylates in particular alkylphenol ethoxylates which contain C 6 -C 4 -alkyl chains and 5 to 30 mol of alkylene oxide / mol.
  • Suitable anionic surfactants are, for example:
  • Sulfated alkoxylated Cs-C 22 -alcohols (alkyl ether sulfates): Compounds of this type are prepared for example by firstly treating a Cs-C 22 -, preferably a C 0 -C 8 alcohol, for example a fatty alcohol alkoxylated and then the alkoxylation sulfated.
  • a Cs-C 22 - preferably a C 0 -C 8 alcohol
  • alkoxylation sulfated for example a fatty alcohol alkoxylated.
  • alkoxylation is preferably used ethylene oxide.
  • Linear C 8 -C 20 -Alkylbenzosulfonate LAS
  • LAS preferably linear C 9 -C 3 alkyl benzenesulfonates and alkyl toluene sulfonates.
  • Soaps such as the Na and K salts of C 8 -C 24 carboxylic acids.
  • the anionic surfactants are preferably added in the form of salts. Suitable cations are for example. Alkali metal ions such as sodium, potassium and lithium, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Particularly suitable cationic surfactants are:
  • Esterquats in particular quaternary esterified mono-, di- and trialkanolamines esterified with C 8 -C 22 -carboxylic acids;
  • R 3 is C r C 4 -alkyl or hydroxy-C r C 4 alkyl
  • R 4 is C 1 -C 4 -alkyl, hydroxyC r C 4 -alkyl or a radical R 4 - (CO) -X- (CH 2 ) P -
  • R 2 is C 7 -C 22 -alkyl
  • Nonionic surfactants are preferably used.
  • the additives are generally from 0.01% to 20% by weight of at least one dispersing agent.
  • suitable dispersants include dispersing, water-soluble polymers (general polyanions) such as polyacrylic acids having a molecular weight of from 1,000 to 100,000 and copolymers of acrylic acid with maleic anhydride having a molecular weight of from 1,000 to 100,000, aromatic sulfonic acid condensates such as phenolsulfonic acid or naphthalenesulfonic acid with formaldehyde.
  • composition used according to the invention may also comprise further components or auxiliaries, depending on the desired application.
  • water-miscible organic solvents In order to improve the removal of fats in the case of pickling degreasing, it may be advantageous to add small amounts of water-miscible organic solvents to the composition according to the invention.
  • the amount of optionally added organic solvents is generally 0 to 10% by weight.
  • suitable Water-miscible solvents include monoalcohols such as methanol, ethanol and propanol, higher alcohols such as ethylene glycol or polyethylene glycols, and ether alcohols such as butyl glycol or methoxypropanol.
  • auxiliaries examples include foam suppressants such as polypropylates or SiIi konether.
  • foam suppressants such as polypropylates or SiIi konether.
  • the type and amount of additional components or auxiliaries are determined by the person skilled in the art according to the intended use.
  • the amount of optionally added further auxiliaries is generally from 0 to 5 wt .-%.
  • the metallic surface is brought into contact with the aqueous composition according to the invention, for example by spraying, dipping or rolling. After a dipping process, you can drain the workpiece to remove excess treatment solution; in the case of metal sheets, metal foils and the like, however, excess treatment solution can also be squeezed off, for example.
  • metallic surfaces can also be treated inside equipment.
  • Deposits in boilers, reactors, pipelines, heat exchangers or the like can be removed by filling or rinsing the equipment with the composition of the invention.
  • the dissolution of coverings can be accelerated by pumping the composition of the invention in the system.
  • the composition according to the invention or the method according to the invention is used for pickling equipment used in oil and gas production.
  • so-called scale deposits in pipelines which may be injection or production drill lines, are removed by means of the composition according to the invention.
  • the composition according to the invention is used for pickling pipes used in so-called acidizing.
  • a further field of application lies in the use of the composition according to the invention for the protection of chemical apparatuses in the case of acid-catalyzed reactions to the attack of acids on metallic components or pipelines of the apparatus.
  • the method according to the invention may optionally comprise one or more pretreatment steps.
  • the metallic surface before the zen be cleaned with the composition of the invention, for example, to remove fats or oils.
  • the method may optionally include post-treatment steps.
  • rinsing steps in which the treated surface is rinsed with suitable cleaning fluids, in particular water, in order to remove, for example, residues of the composition according to the invention from the surface may be mentioned here.
  • the treatment during the process according to the invention can be carried out batchwise or continuously.
  • a continuous process is particularly suitable for treating strip metals.
  • the metal strip is thereby driven through a tub or a rinsing device and optionally through further pre- and post-treatment stations.
  • Temperature and duration of treatment are determined by the skilled person depending on the desired application. A higher temperature speeds up the one hand, the pickling attack on the to be solved unwanted layers, on the other hand also the pickling attack on the metal itself.
  • the inventive method at a temperature in the range of 60 to 90 0 C preferably at a temperature in the range is carried out from 80 to 90 0 C.
  • the treatment duration can be from 1 second to several hours.
  • a temperature of 60 to 80 0 C, for example 70 0 C, with contact times of 1 to 10 seconds has proven particularly useful.
  • test plates made of steel 1.0037 with a dimension of 20x50x1 mm were alkaline, electrolytically cleaned, in each case immersed in a test solution (see solutions 1 to 5) for 24 hours at 40 0 C and the area-related mass loss determined by differential gravimetric gravimetric.
  • a solution of the degreasing bath of the following composition is used in a plastic tub with two flat electrodes (stainless steel or graphite) which are larger than the test sheet:
  • EDTA ethylenediaminetetraacetic acid
  • non-ionic surfactant alkylphenol, ethoxylated, on average 10 ethylene oxide
  • De-rusting A solution of the de-rusting bath of the following composition is used in a plastic trough with two flat electrodes which are larger than the test sheet: 100 g of diammonium citrate in 1000 ml of water
  • a steel sheet of size 20 mm x 50 mm x 1 mm is wiped with a paper towel and immersed at 10 volts in the degreasing between the electrodes and connected as a cathode.
  • the voltage is set so that the current is 1 ampere (A).
  • the steel sheet is removed and rinsed under running water for 5 seconds.
  • the steel sheet is immersed at 10 volts in the de-rusting bath to the electrodes and connected as a cathode.
  • the voltage is adjusted so that the current is 1 ampere (A).
  • the steel sheet is removed and rinsed for 5 seconds under running deionised water, blown off with air and immediately used for testing.
  • the metal sheet of size 20 mm x 50 mm x 1 mm is electrolytically degreased and de-rusted.
  • the analysis mass determines the initial mass.
  • the metal sheet is used immediately after weighing.
  • the prepared metal sheet is placed diagonally in a 200 ml glass bottle with test solution.
  • the angle between steel sheet and floor is 35 °.
  • the glass bottle is tightly closed and stored at room temperature. During storage, the glass bottle is shaken once every 6 hours.
  • the metal sheet is removed from the solution, rinsed with deionized water, brushed off with steel wool, rinsed with deionised water and blown dry with air. Then the mass is determined.
  • Korantin ® PM is available from BASF SE, a Propargylalkoholethoxylat having an average of one ethylene oxide unit
  • Pluriol E ® 300 available from BASF SE is a polyethylene glycol having an average molecular weight of 300 g / mol
  • Pluriol ® E 600 available from BASF SE is a polyethylene glycol having an average molecular weight of 600 g / mol
  • Pluriol ® E 1000 available from BASF SE is a polyethylene glycol having an average molecular weight of 1000 g / mol
  • Pluriol E ® 1500 available from BASF SE is a polyethylene glycol having an average molecular weight of 1500 g / mol
  • Figure 1 shows that the corrosion is significantly inhibited by the corrosion inhibitor used in the invention, not only in comparison to a sample without corrosion inhibitor, but also in comparison with a commercial corrosion inhibitor Korantin ® PM.

Abstract

L'invention concerne une composition aqueuse acide contenant un thiodiglycolalcoxylate, destinée au traitement de surfaces métalliques. L'invention concerne également l'utilisation d'un ou plusieurs composés représentés par la formule (I) en tant qu'inhibiteurs de corrosion.
EP09751935A 2008-11-17 2009-11-16 Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion Withdrawn EP2358924A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09751935A EP2358924A2 (fr) 2008-11-17 2009-11-16 Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08169230 2008-11-17
PCT/EP2009/065232 WO2010055160A2 (fr) 2008-11-17 2009-11-16 Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion
EP09751935A EP2358924A2 (fr) 2008-11-17 2009-11-16 Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion

Publications (1)

Publication Number Publication Date
EP2358924A2 true EP2358924A2 (fr) 2011-08-24

Family

ID=41796122

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09751935A Withdrawn EP2358924A2 (fr) 2008-11-17 2009-11-16 Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion

Country Status (3)

Country Link
US (1) US8901060B2 (fr)
EP (1) EP2358924A2 (fr)
WO (1) WO2010055160A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939146B1 (fr) 2008-11-28 2012-11-16 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
EP2492372A1 (fr) * 2011-02-23 2012-08-29 Enthone, Inc. Solution aqueuse et procédé pour la formation d'une couche de passivation
CA2834109C (fr) 2011-05-03 2020-02-11 Atotech Deutschland Gmbh Bain et procede d'electroplacage pour la production de couches de chrome noir
US20140119984A1 (en) * 2012-10-29 2014-05-01 Halliburton Energy Services, Inc. Withanolide corrosion inhibitor for carbon steel
WO2017031162A1 (fr) 2015-08-20 2017-02-23 Dow Global Technologies Llc Lubrifiant comprenant du polyalkylène glycol contenant du soufre
DE102017207237A1 (de) * 2016-04-29 2017-11-02 Chemetall Gmbh Verfahren zur korrosionsschützenden Behandlung einer metallischen Oberfläche mit vermindertem Beizabtrag
RU2747720C2 (ru) 2016-04-29 2021-05-13 Хеметалл Гмбх Композиция для уменьшения удаления материала путем травления при травлении металлических поверхностей, включающих оцинкованную и/или непокрытую сталь
JP2019522706A (ja) 2016-06-24 2019-08-15 ダウ グローバル テクノロジーズ エルエルシー 潤滑剤組成物
CN109312249B (zh) 2016-06-24 2021-12-31 陶氏环球技术有限责任公司 润滑剂组合物
FR3070694B1 (fr) 2017-09-01 2020-07-03 Arkema France Inhibiteurs de corrosion metallique
WO2023111687A1 (fr) 2021-12-17 2023-06-22 Cci Holdings, Inc. Système de transfert de chaleur à inhibiteurs organiques non ioniques compatibles avec une exposition au flux dans des opérations de pile à combustible

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1780594A (en) * 1929-10-09 1930-11-04 Grasselli Chemical Co Acid treatment of metal articles
US2518245A (en) * 1946-08-24 1950-08-08 Shell Dev Process for preparing copolymers from alkylene glycols and di(hydroxyalkyl) sulfides
US2858274A (en) * 1954-03-16 1958-10-28 Exxon Research Engineering Co Thio formal synthetic lubricants
US3470146A (en) * 1967-05-26 1969-09-30 Sinclair Koppers Co Suspension polymerization of vinyl aromatic monomers
US3997614A (en) * 1972-10-25 1976-12-14 Reichhold Chemicals, Inc. Polythiaformals
US4266080A (en) 1978-02-02 1981-05-05 Ciba-Geigy Corporation Perfluoroalkylthioethyl ether derivatives
GB2039299B (en) 1978-12-26 1983-05-25 Rohco Inc Brightening and levelling agent for acid zinc plating baths
US4832802A (en) * 1988-06-10 1989-05-23 Mcgean-Rohco, Inc. Acid zinc-nickel plating baths and methods for electrodepositing bright and ductile zinc-nickel alloys and additive composition therefor
DE4021694A1 (de) * 1990-07-07 1992-01-09 Henkel Kgaa Neue thiodiglykolalkxylat-derivate, verfahren zu ihrer herstellung und ihre verwendung als weichmacher fuer textilien
DE69110208T2 (de) * 1990-08-03 1995-10-19 Rohco Inc Mcgean Kupferplattieren von Tiefdruckzylindern.
DE4204885A1 (de) * 1992-02-19 1993-08-26 Henkel Kgaa Thiodiglykol-derivate, verfahren zu ihrer herstellung und deren verwendung zum weichmachen von textilien
JPH10130873A (ja) 1996-10-25 1998-05-19 Nippon Shokubai Co Ltd 金属腐食抑制剤およびそれを含む金属腐食抑制液並びにそれを用いた金属腐食抑制方法
US5976416A (en) * 1997-05-13 1999-11-02 Halliburton Energy Services, Inc. Corrosion inhibited organic acid compositions and methods
KR20060090817A (ko) 2003-09-30 2006-08-16 바스프 악티엔게젤샤프트 알콕시화된 알키놀을 사용하여 금속 표면을 산세하는 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2010055160A2 (fr) 2010-05-20
WO2010055160A3 (fr) 2010-08-19
US8901060B2 (en) 2014-12-02
US20110232679A1 (en) 2011-09-29

Similar Documents

Publication Publication Date Title
EP2358924A2 (fr) Utilisation de thioglycoléthoxylate en tant qu'inhibiteur de corrosion
WO2005033364A1 (fr) Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
AT393688B (de) Saures, fluessiges reinigungsmittel fuer keramikplatten und verfahren zu seiner herstellung
EP1817398B1 (fr) Produit nettoyant pour metaux contenant un polyethylene imine
DE3316724A1 (de) Mittel und verfahren zur reinigung und passivierung von metallen im spritzverfahren
DE1937841A1 (de) Verfahren zur Reinigung von Aluminium-Oberflaechen vor dem Lackieren
DE10345801A1 (de) Verfahren zum Beizen metallischer Oberflächen unter Verwendung von alkoxylierten Alkinolen
DE3229018A1 (de) Grill- und backofen-reinigungsmittel
DE10349728A1 (de) Im wesentlichen Chrom-freies Verfahren zum Passivieren von metallischen Oberflächen aus Zn, Zn-Legierungen, AI oder AI-Legierungen
EP1809791B1 (fr) Procede d'elimination de battitures provenant de laser
DE2758629C3 (de) Verfahren zum Reinigen der verzinnten Oberfläche eines eisenhaltigen Metalls
DE2617175A1 (de) Schmiermittelgemisch auf wasserbasis
EP2625312A1 (fr) Procédé de passivation de surfaces métalliques avec des compositions aqueuses contenant des agents tensioactifs
DE69932035T2 (de) Verfahren zur behandlung eines metallproduktes
EP0231524B1 (fr) Application d'acides alkylbenzoylacryliques comme inhibiteurs de corrosion
DE4102709C1 (en) Degreasing metal surfaces using aq. prepn. - contg. biologically degradable adducts of lower alkylene oxide(s), fatty alcohol(s) and cationic surfactants
DE2921572A1 (de) Phosphorsaeureester des poly(2-10)- aethylenoxy-n-butan-1,4-diols
DE2041871B2 (de) Verfahren zur Vorbehandlung von Rost aufweisenden, eisenhaltigen Oberflächen für die elektrophoretische Lackierung
DE2315437C2 (de) Verfahren zur Vorbehandlung von Stahlbandoberflächen vor dem Glühen
DE1210296B (de) Mittel und Verfahren zur Behandlung von Metallen fuer die Kaltverformung
WO2022017564A1 (fr) Procédé pour éliminer un produit de corrosion d'une surface métallique
EP3947773A1 (fr) Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit
WO1993006200A1 (fr) Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants
DE2305821A1 (de) Pulverfoermige saure metallreinigungsmittel
DE1908421A1 (de) Mittel zum Abloesen von kupferhaltigen Metallueberzuegen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110617

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170215

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170627