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EP2971245B1 - Method to control corrosion of a metal surface using alkyl sulfamic acids or salts thereof - Google Patents

Method to control corrosion of a metal surface using alkyl sulfamic acids or salts thereof Download PDF

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Publication number
EP2971245B1
EP2971245B1 EP14714121.2A EP14714121A EP2971245B1 EP 2971245 B1 EP2971245 B1 EP 2971245B1 EP 14714121 A EP14714121 A EP 14714121A EP 2971245 B1 EP2971245 B1 EP 2971245B1
Authority
EP
European Patent Office
Prior art keywords
metal surface
sulfamic acid
salt
alkyl
corrosion
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.)
Not-in-force
Application number
EP14714121.2A
Other languages
German (de)
French (fr)
Other versions
EP2971245A1 (en
Inventor
Jesse Pokrzywinski
Marilyn Whittemore
Thomas E. Mcneel
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Buckman Laboratories International Inc
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Buckman Laboratories International Inc
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Publication of EP2971245A1 publication Critical patent/EP2971245A1/en
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Publication of EP2971245B1 publication Critical patent/EP2971245B1/en
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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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • 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
    • 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
    • C23F11/163—Sulfonic acids
    • 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
    • C23F11/164—Sulfur-containing compounds containing a -SO2-N group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • the present invention relates to the inhibition of corrosion of a metal surface using one or more anti-corrosion agents.
  • Corrosion has been the subject of scientific study for more than 150 years. Corrosion is a naturally occurring phenomenon that relates to the deterioration of a material or its properties because of a reaction with its environment. In addition to reduced longevity, corrosion also produces oxides that can further deteriorate a system by erosion, plugging, and fouling. Oxides can deposit on heat transfer surfaces, reducing efficiency, and increasing energy costs. Common sources of corrosion include dissolved oxygen, bacteria, electrolysis (stray current), differential metal (dielectric), and differential cells. Flow, temperature, and pressure can effect the corrosion rate.
  • Corrosion inhibitors are used in oil and gas exploration and production, petroleum refining, chemical manufacturing, heavy manufacturing, water treatment, and the product additive industries. As products and manufacturing processes have become more complex and the consequences of corrosion more costly, greater attention is being given to the control and prevention of corrosion. Thus, there is a continued need to identify more effective corrosion inhibitors that minimize financial and environmental costs with better toxicological profiles.
  • a feature of the present invention is to inhibit corrosion of a metal surface.
  • Another feature of this invention is to provide methods of using an anti-corrosion agent having low toxicity and/or high efficacy to prevent or minimize the corrosion of metal surfaces.
  • the present invention provides a method of inhibiting corrosion of a metal surface including applying at least one alkyl sulfamic acid or salt thereof to the metal surface in an amount of 1.0 to 50 ppm to inhibit corrosion of the metal surface.
  • At least one alkyl sulfamic acid or salt thereof can be applied in any suitable manner to the metal surface, for example, the application can include one or more of the following: flowing, coating, sponging, wiping, spraying, painting, showering, and misting.
  • the method can further include subjecting the treated metal surface with corrosive agent(s).
  • the present invention provides a method of inhibiting corrosion of a metal surface including applying at least one alkyl sulfamic acid or salt thereof or a solution containing the alkyl sulfamic acid or salt, to the metal surface in an amount of 1.0 to 50 ppm to inhibit corrosion of the metal surface.
  • Any type of corrosion can be inhibited as characterized by cause and/or effect.
  • the corrosion can include uniform corrosion that extends evenly across the surface, pitting corrosion that is uneven and has smaller deep areas (pits), exfoliation corrosion that moves along layers of elongated grains, and/or intergranular corrosion that grows along grain boundaries.
  • any suitable or desirable alkylated derivative of sulfamic acid, salt thereof, combinations thereof can be used in the present invention. More than one alkylated derivative of sulfamic acid or salt thereof can be used.
  • Sulfamic acid is also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, and sulfamidic acid.
  • Sulfamic acid is a molecular compound having the formula H 3 NSO 3 .
  • Sulfamates can be O-substituted, N-substituted-, or di-/tri-substituted derivatives of sulfamic acid and are also considered to be sulfamic acids or salts thereof for purposes of the present invention. Both tautomers H 3 NSO 3 and H 2 NSO 2 (OH) fall within the scope of sulfamic acids or salts thereof in the present invention. Alkylated derivatives of these sulfamic acids can be used.
  • the alkylated derivative of sulfamic acid can thus be an alkyl sulfamic acid or salt thereof.
  • the alkyl group can contain any desirable number of carbons in a linear, branched, and/or cyclic configuration.
  • the alkyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and the like.
  • the at least one sulfamic acid can have the formula R 1 R 2 NS(O) 2 (OH), and, for example, R 1 and R 2 are independently a hydrogen, a C 4 - C 20 alkyl group, or a cycloalkyl group, and R 1 and R 2 are not both hydrogen, and/or R 1 , R 2 , and the N form a 5-8 membered heterocyclic ring including one or more of O, NH, and CH 2 .
  • the at least one alkyl sulfamic acid can have the formula R 1 R 2 NS(O) 2 (OH) and, for example, R 1 and R 2 can independently be a hydrogen, a C 4 - C 20 alkyl group, or a cycloalkyl group, and R 1 and R 2 are not both hydrogen.
  • the at least one alkyl sulfamic acid can have the formula R 1 R 2 NS(O) 2 (OH), and, for example, R 1 or R 2 , but not both, is a C 4 - C 20 alkyl group or a cycloalkyl group.
  • the at least one alkyl sulfamic acid can have the formula R 1 R 2 NS(O) 2 (OH) and, for example, both R 1 and R 2 are a C 4 - C 20 alkyl group or cycloalkyl group.
  • the at least one alkyl sulfamic acid can have the formula R 1 R 2 NS(O) 2 (OH) and, for example, R 1 , R 2 , and the N form a 5-8 membered heterocyclic ring including one or more of O, NH, and CH 2 .
  • the sulfamic acid or salt thereof can be a halide derivative of a sulfamic acid.
  • Salts include, but are not limited to, alkali metal and quaternary ammonium salts. Methods for the preparation of various sulfamic acids or salts thereof are described in Nickless, Inorganic Sulphur Chemistry, Elsevier Publishing Company, New York; 611-614 (1968 ).
  • the alkyl sulfamic acid or salt thereof can be applied by itself to a metal surface or applied as part of a fluid that can optionally contain one or more additional components, for example, an additional anti-corrosion agent and/or a biocide. When combined with one or more additional anti-corrosion agents, the resulting corrosion inhibition can be sub-additive, additive, or super-additive (synergistic).
  • the fluid can include a liquid, a vapor (gas), or a combination thereof.
  • the fluid can include H 2 O, NH 3 , and/or an alcohol.
  • the fluid can be aqueous, non-aqueous, or both.
  • the fluid can include an acid or base in addition to the alkyl sulfamic acid or salt thereof.
  • the fluid can include a salt solution of at least one salt independent of an alkyl sulfamic acid salt.
  • the fluid containing the alkyl sulfamic acid or salt thereof can be cooled or heated, or be used at ambient temperature or other temperatures above or below 20 deg C.
  • the pH of the fluid can be neutral or from about 0.0 to about 14, from about 2.0 to about 12, from about 4.0 to about 10, or from about 6.0 to about 8.0.
  • the concentration of the at least one alkyl sulfamic acid or salt thereof can be adjusted according to the particular metal surface(s) being treated and the parameters of the system in which it is employed.
  • the concentration of at least one alkyl sulfamic acid or salt thereof in a fluid system can be from 1.0 ppm to 50 ppm, or from 1.0 ppm to about 25 ppm, or from 1.0 ppm to about 15 ppm, or from 1.0 ppm to about 10 ppm, or from 1.0 ppm to about 5 ppm.
  • the alkyl sulfamic acid or salt thereof can be prepared as a stock solution of from about 0.01 wt% to about 100 wt%, from about 0.1 wt% to about 95 wt%, from about 1.0 wt% to about 80 wt%, from about 5.0 wt% to about 75 wt%, from about 10 wt% to about 60 wt%, from about 15 wt% to about 50 wt% from about 25wt% to about 40 wt% alkyl sulfamic acid or salt thereof based on the total weight of the stock solution.
  • the alkyl sulfamic acid or salt thereof can be used in the methods of the invention as a solid, liquid, and/or gaseous formulation.
  • the methods according to the invention can be part of an overall water treatment regimen.
  • the alkyl sulfamic acid or salt thereof can be used with other water treatment chemicals, such as biocides (e.g., algicides, fungicides, bactericides, molluscicides, oxidizers, etc.), stain removers, clarifiers, flocculants, coagulants, or other chemicals commonly used in water treatment.
  • biocides e.g., algicides, fungicides, bactericides, molluscicides, oxidizers, etc.
  • stain removers e.g., clarifiers, flocculants, coagulants, or other chemicals commonly used in water treatment.
  • a composition containing alkyl sulfamic acid or salt thereof according to the present invention can be prepared in various forms known in the art.
  • the composition can be prepared in liquid form as a solution, dispersion, emulsion, suspension, or paste; a dispersion, suspension, or paste in a non-solvent; or as a solution by dissolving the alkyl sulfamic acid or salt thereof in a solvent or combination of solvents.
  • Suitable solvents include, but are not limited to, acetone, glycols, alcohols, ethers, water, or other water-dispersible solvents.
  • the composition can be prepared as a liquid concentrate for dilution prior to its intended use.
  • composition of the invention can be solubilized by simple agitation.
  • a composition of the present invention can be prepared in solid form.
  • the alkyl sulfamic acid or salt thereof can be formulated as a powder or tablet using means known in the art.
  • the tablets can contain a variety of excipients known in the tableting art such as dyes or other coloring agents.
  • Other components known in the art such as fillers, binders, glidants, lubricants, or antiadherents can be included. These components can be included to improve tablet properties and/or the tableting process.
  • the alkyl sulfamic acid, salt thereof, and/or composition including the same can be applied directly or indirectly to a metal surface using any appropriate technique, for example flowing, coating, sponging, wiping, spraying, painting, showering, and/or misting of the at least one alkyl sulfamic acid or salt thereof to the metal surface can be employed.
  • the "applying" can include flowing a fluid containing the at least one alkyl sulfamic acid or salt thereof over the metal surface.
  • the method can comprise forming a protective film on the metal surface including the at least one alkyl sulfamic acid or salt thereof.
  • any suitable metal surface can be inhibited using the methods of the invention. Any metal, combination of metals, or alloys can be protected. Even surfaces that contain minor amounts or trace amounts of one or metals can be protected.
  • the metal can be any metal susceptible to corrosion including industrial metals.
  • metal surfaces include those containing one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium , zirconium, platinum, gold, mercury, niobium, iridium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, aluminum, indium, germanium, gallium, antimony, tin, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and/or ytterbium and/or alloys of one or more of these metals.
  • Alloy metals such as stainless steel, steel, mild steel, bronze, brass, and the like are further examples of metals.
  • the metal surface can be a ferrous or a non-ferrous surface. The surface can have any shape and/or dimensions.
  • the metal surface can be continuous or discontinuous.
  • the metal can be embedded in one or more non-metal media such as a plastic, a rubber, a glass, a ceramic, a composite, or the like.
  • the metal can be electroplated.
  • the metal can be galvanized. A constant or variable electric current and/or magnetic field can be applied to the metal surface.
  • the metal surface can be heated or cooled.
  • the method of the invention can further include contacting the metal surface with at least one corrosive agent from which protection is sought.
  • the applying of the alkyl sulfamic acid, salt thereof, and/or one or more other anti-corrosive agents can be performed before, during, and/or after the contacting of the metal surface with the at least one corrosive agent.
  • the metal surface can be part of a closed fluid system or an open fluid system, or both.
  • Examples of systems that can be treated include, but are not limited to cooling systems, heating systems, cooling towers, boilers, radiators, steam piping, oil transport machinery and piping, oil production machinery and piping, paper and pulp machinery, drinking and tap water treatment plants, plumbing, sewers, waste water treatment plants, and other industrial uses that come in contact with corrosive agents.
  • the invention results in a lower degree of chemical change of the metal surface in the presence of an anti-corrosion inhibitor than in its absence.
  • Corrosion inhibition can be partial inhibition or complete inhibition.
  • the chemical change can be measured, for example, by measuring a change in weight of the metal surface and/or by measuring the concentration of metal, ions thereof, or salts thereof originating from the metal surface in fluid that flows past the metal surface.
  • the weight loss, for example, of a corrosion coupon after exposure to a corrosive environment can be expressed as mils (thousandths of an inch) per year penetration (MPY). 1 MPY is equal to 0.0254 mm/y, which is equal to 25.4 ⁇ m/y.
  • the corrosion rate can be calculated with the assumption of uniform corrosion over the entire surface of the coupon.
  • Metal corrosion can occur via electrochemical reactions at the interface between a metal and an electrolyte solution. A thin film of moisture on a metal surface forms the electrolyte for atmospheric corrosion. Corrosion normally occurs at a rate determined by an equilibrium between opposing electrochemical reactions, anodic (metal oxidation) and cathodic (reduction of a solution species). These reactions can occur on one metal or on two or more dissimilar metals that are in electrical communication. Corrosion current can be used to generate a corrosion rate by assuming an electrolytic dissolution reaction involving a chemical species. Uniform corrosion across a metal surface allows calculation of the corrosion rate in units of distance per year. For an alloy undergoing uniform dissolution, equivalent weight is a weighted average of the equivalent weights of the alloy components. If the dissolution is not uniform, corrosion products can be used to calculate equivalent weight.
  • a weight loss can be converted to a corrosion rate with knowledge of the density and the sample area of a sample.
  • ASTM Standard G 102 Standard Practice for Calculation of Corrosion Rates and Related Information from Electrochemical Measurements can be used.
  • An eddy current instrument and probe can be used for measuring corrosion by monitoring a conductivity curve and impedance plane and using one or more techniques such as single layer corrosion detection, two layer corrosion detection, a limited penetration method, dual frequency method, and/or a variable frequency method.
  • Copper metal sample coupons with a surface area of 3.38 in 2 (21.8 cm 2 ) were installed in a laboratory-scale liquid recirculating loop equipped with a reservoir capable of holding approximately 11 L total volume.
  • the apparatus was designed to hold metal sample coupons in the path of flowing liquid at a chosen flow rate and temperature for chosen period of time. After exposure for an adequate period of time, the metal sample weight loss resulting from corrosion was used to calculate the corrosion rate.
  • the exact conditions of the tests are listed in the Tables 1-3. For tests shown in all three tables, the temperature was 35°C, linear velocity was 7 gallons per minute (26.5 L/min, i.e. 3 ft/s or approximately 1 m/s), and the mass of treatment was 10 L. Synthetic water was used having 1170 ppm NaCl and 505 ppm NaHCO 3 , at pH 8.
  • corrosion coupons were cleaned with an acidic solution that is capable of removing various chemical and biological deposits and films that might have formed on the coupon surface during exposure to the test environment.
  • the weight change (and corresponding corrosion rate) determined before a coupon has been chemically cleaned helps the researcher ascertain general material removal and/or deposition process information.
  • the corrosion rate obtained after cleaning is considered the true corrosion rate for the system under evaluation. Comparative data from known corrosion inhibitors and/or untreated systems collected at the time of the subject inhibitor evaluation are advantageous due to variability in experimental factors that otherwise are not easily controlled between different experiments.
  • the MPY milli-inch per year
  • ⁇ m/yr of corrosion were determined.
  • Tables 1-3 show that hexylsulfamic acid has corrosion inhibitor properties that result in copper corrosion rates far less than that obtained in untreated systems.
  • the data also show that the copper corrosion inhibition performance of hexylsulfamic acid is similar to that obtained for tolyltriazole.
  • the data also show that hexylsulfamic acid performance as a copper corrosion inhibitor has an inverse relationship with inhibitor concentration under the given test conditions, which is similar to the performance trend obtained with tolyltriazole. Put another way, lower dosages, treatment levels, were more effective in controlling corrosion than higher dosages.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)

Description

    BACKGROUND OF THE INVENTION
  • This application claims the benefit of prior U.S. Provisional Patent Application No. 61/783,706, filed March 14, 2013 .
  • The present invention relates to the inhibition of corrosion of a metal surface using one or more anti-corrosion agents.
  • Corrosion has been the subject of scientific study for more than 150 years. Corrosion is a naturally occurring phenomenon that relates to the deterioration of a material or its properties because of a reaction with its environment. In addition to reduced longevity, corrosion also produces oxides that can further deteriorate a system by erosion, plugging, and fouling. Oxides can deposit on heat transfer surfaces, reducing efficiency, and increasing energy costs. Common sources of corrosion include dissolved oxygen, bacteria, electrolysis (stray current), differential metal (dielectric), and differential cells. Flow, temperature, and pressure can effect the corrosion rate.
  • Corrosion inhibitors are used in oil and gas exploration and production, petroleum refining, chemical manufacturing, heavy manufacturing, water treatment, and the product additive industries. As products and manufacturing processes have become more complex and the consequences of corrosion more costly, greater attention is being given to the control and prevention of corrosion. Thus, there is a continued need to identify more effective corrosion inhibitors that minimize financial and environmental costs with better toxicological profiles.
    • SUMMARY OF THE INVENTION
  • A feature of the present invention is to inhibit corrosion of a metal surface.
  • Another feature of this invention is to provide methods of using an anti-corrosion agent having low toxicity and/or high efficacy to prevent or minimize the corrosion of metal surfaces.
  • Methods of inhibiting the corrosion of metal surfaces located in a variety of different systems and environments are also features of this invention.
  • To achieve these and other advantages and in accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention provides a method of inhibiting corrosion of a metal surface including applying at least one alkyl sulfamic acid or salt thereof to the metal surface in an amount of 1.0 to 50 ppm to inhibit corrosion of the metal surface. At least one alkyl sulfamic acid or salt thereof can be applied in any suitable manner to the metal surface, for example, the application can include one or more of the following: flowing, coating, sponging, wiping, spraying, painting, showering, and misting. The method can further include subjecting the treated metal surface with corrosive agent(s).
  • Additional features and advantages of the present invention will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The objectives and other advantages of the present invention will be realized and obtained by means of the elements and combinations particularly pointed out in the written description and appended claims.
  • It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are only intended to provide a further explanation of the present invention, as claimed.
    • DETAILED DESCRIPTION OF THE PRESENT INVENTION
  • The present invention provides a method of inhibiting corrosion of a metal surface including applying at least one alkyl sulfamic acid or salt thereof or a solution containing the alkyl sulfamic acid or salt, to the metal surface in an amount of 1.0 to 50 ppm to inhibit corrosion of the metal surface. Any type of corrosion can be inhibited as characterized by cause and/or effect. For example, the corrosion can include uniform corrosion that extends evenly across the surface, pitting corrosion that is uneven and has smaller deep areas (pits), exfoliation corrosion that moves along layers of elongated grains, and/or intergranular corrosion that grows along grain boundaries.
  • Any suitable or desirable alkylated derivative of sulfamic acid, salt thereof, combinations thereof can be used in the present invention. More than one alkylated derivative of sulfamic acid or salt thereof can be used. Sulfamic acid is also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, and sulfamidic acid. Sulfamic acid is a molecular compound having the formula H3NSO3. Sulfamates can be O-substituted, N-substituted-, or di-/tri-substituted derivatives of sulfamic acid and are also considered to be sulfamic acids or salts thereof for purposes of the present invention. Both tautomers H3NSO3 and H2NSO2(OH) fall within the scope of sulfamic acids or salts thereof in the present invention. Alkylated derivatives of these sulfamic acids can be used.
  • The alkylated derivative of sulfamic acid can thus be an alkyl sulfamic acid or salt thereof. The alkyl group can contain any desirable number of carbons in a linear, branched, and/or cyclic configuration. For example, the alkyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and the like. The at least one sulfamic acid can have the formula R1R2NS(O)2(OH), and, for example, R1 and R2 are independently a hydrogen, a C4 - C20 alkyl group, or a cycloalkyl group, and R1 and R2 are not both hydrogen, and/or R1, R2, and the N form a 5-8 membered heterocyclic ring including one or more of O, NH, and CH2. The at least one alkyl sulfamic acid can have the formula R1R2NS(O)2(OH) and, for example, R1 and R2 can independently be a hydrogen, a C4 - C20 alkyl group, or a cycloalkyl group, and R1 and R2 are not both hydrogen. The at least one alkyl sulfamic acid can have the formula R1R2NS(O)2(OH), and, for example, R1 or R2, but not both, is a C4 - C20 alkyl group or a cycloalkyl group. The at least one alkyl sulfamic acid can have the formula R1R2NS(O)2(OH) and, for example, both R1 and R2 are a C4 - C20 alkyl group or cycloalkyl group. The at least one alkyl sulfamic acid can have the formula R1R2NS(O)2(OH) and, for example, R1, R2, and the N form a 5-8 membered heterocyclic ring including one or more of O, NH, and CH2. The sulfamic acid or salt thereof can be a halide derivative of a sulfamic acid. Examples of sulfamic acids and salts thereof that can be alkylated (if not so already) employed in the method of the present invention include those described in U.S. Patent Nos. 7,576,041 ; 7,470,652 ; 7,345,202 ; 6,983,614 ; 6,824,668 ; 6,380,182 ; 6,110,387 ; 6,103,131 ; 5,478,461 ; 5,431,839 ; 4,386,060 ; 4,327,034 ; 4,049,709 ; 3,223,704 ; and 3,536,759 . Salts include, but are not limited to, alkali metal and quaternary ammonium salts. Methods for the preparation of various sulfamic acids or salts thereof are described in Nickless, Inorganic Sulphur Chemistry, Elsevier Publishing Company, New York; 611-614 (1968).
  • The alkyl sulfamic acid or salt thereof can be applied by itself to a metal surface or applied as part of a fluid that can optionally contain one or more additional components, for example, an additional anti-corrosion agent and/or a biocide. When combined with one or more additional anti-corrosion agents, the resulting corrosion inhibition can be sub-additive, additive, or super-additive (synergistic). The fluid can include a liquid, a vapor (gas), or a combination thereof. The fluid can include H2O, NH3, and/or an alcohol. The fluid can be aqueous, non-aqueous, or both. The fluid can include an acid or base in addition to the alkyl sulfamic acid or salt thereof. The fluid can include a salt solution of at least one salt independent of an alkyl sulfamic acid salt.
  • The fluid containing the alkyl sulfamic acid or salt thereof can be cooled or heated, or be used at ambient temperature or other temperatures above or below 20 deg C. The pH of the fluid can be neutral or from about 0.0 to about 14, from about 2.0 to about 12, from about 4.0 to about 10, or from about 6.0 to about 8.0.
  • The concentration of the at least one alkyl sulfamic acid or salt thereof can be adjusted according to the particular metal surface(s) being treated and the parameters of the system in which it is employed. The concentration of at least one alkyl sulfamic acid or salt thereof in a fluid system can be from 1.0 ppm to 50 ppm, or from 1.0 ppm to about 25 ppm, or from 1.0 ppm to about 15 ppm, or from 1.0 ppm to about 10 ppm, or from 1.0 ppm to about 5 ppm. The alkyl sulfamic acid or salt thereof can be prepared as a stock solution of from about 0.01 wt% to about 100 wt%, from about 0.1 wt% to about 95 wt%, from about 1.0 wt% to about 80 wt%, from about 5.0 wt% to about 75 wt%, from about 10 wt% to about 60 wt%, from about 15 wt% to about 50 wt% from about 25wt% to about 40 wt% alkyl sulfamic acid or salt thereof based on the total weight of the stock solution. The alkyl sulfamic acid or salt thereof can be used in the methods of the invention as a solid, liquid, and/or gaseous formulation. The methods according to the invention can be part of an overall water treatment regimen. The alkyl sulfamic acid or salt thereof can be used with other water treatment chemicals, such as biocides (e.g., algicides, fungicides, bactericides, molluscicides, oxidizers, etc.), stain removers, clarifiers, flocculants, coagulants, or other chemicals commonly used in water treatment.
  • Depending on its use, a composition containing alkyl sulfamic acid or salt thereof according to the present invention can be prepared in various forms known in the art. For example, the composition can be prepared in liquid form as a solution, dispersion, emulsion, suspension, or paste; a dispersion, suspension, or paste in a non-solvent; or as a solution by dissolving the alkyl sulfamic acid or salt thereof in a solvent or combination of solvents. Suitable solvents include, but are not limited to, acetone, glycols, alcohols, ethers, water, or other water-dispersible solvents. The composition can be prepared as a liquid concentrate for dilution prior to its intended use. Common additives such as surfactants, emulsifiers, dispersants, and the like can be used as known in the art to increase the solubility of the alkyl sulfamic acid or its salt as well as other components in a liquid composition or system, such as an aqueous composition or system. The composition of the invention can be solubilized by simple agitation.
  • A composition of the present invention can be prepared in solid form. For example, the alkyl sulfamic acid or salt thereof can be formulated as a powder or tablet using means known in the art. The tablets can contain a variety of excipients known in the tableting art such as dyes or other coloring agents. Other components known in the art such as fillers, binders, glidants, lubricants, or antiadherents can be included. These components can be included to improve tablet properties and/or the tableting process.
  • The alkyl sulfamic acid, salt thereof, and/or composition including the same can be applied directly or indirectly to a metal surface using any appropriate technique, for example flowing, coating, sponging, wiping, spraying, painting, showering, and/or misting of the at least one alkyl sulfamic acid or salt thereof to the metal surface can be employed. The "applying" can include flowing a fluid containing the at least one alkyl sulfamic acid or salt thereof over the metal surface. The method can comprise forming a protective film on the metal surface including the at least one alkyl sulfamic acid or salt thereof.
  • The corrosion of any suitable metal surface can be inhibited using the methods of the invention. Any metal, combination of metals, or alloys can be protected. Even surfaces that contain minor amounts or trace amounts of one or metals can be protected. The metal can be any metal susceptible to corrosion including industrial metals. Examples of metal surfaces include those containing one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium , zirconium, platinum, gold, mercury, niobium, iridium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, aluminum, indium, germanium, gallium, antimony, tin, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and/or ytterbium and/or alloys of one or more of these metals. Alloy metals such as stainless steel, steel, mild steel, bronze, brass, and the like are further examples of metals. The metal surface can be a ferrous or a non-ferrous surface. The surface can have any shape and/or dimensions. The metal surface can be continuous or discontinuous. The metal can be embedded in one or more non-metal media such as a plastic, a rubber, a glass, a ceramic, a composite, or the like. The metal can be electroplated. The metal can be galvanized. A constant or variable electric current and/or magnetic field can be applied to the metal surface. The metal surface can be heated or cooled.
  • The method of the invention can further include contacting the metal surface with at least one corrosive agent from which protection is sought. The applying of the alkyl sulfamic acid, salt thereof, and/or one or more other anti-corrosive agents can be performed before, during, and/or after the contacting of the metal surface with the at least one corrosive agent. The metal surface can be part of a closed fluid system or an open fluid system, or both. Examples of systems that can be treated include, but are not limited to cooling systems, heating systems, cooling towers, boilers, radiators, steam piping, oil transport machinery and piping, oil production machinery and piping, paper and pulp machinery, drinking and tap water treatment plants, plumbing, sewers, waste water treatment plants, and other industrial uses that come in contact with corrosive agents.
  • The invention results in a lower degree of chemical change of the metal surface in the presence of an anti-corrosion inhibitor than in its absence. Corrosion inhibition can be partial inhibition or complete inhibition. The chemical change can be measured, for example, by measuring a change in weight of the metal surface and/or by measuring the concentration of metal, ions thereof, or salts thereof originating from the metal surface in fluid that flows past the metal surface. The weight loss, for example, of a corrosion coupon after exposure to a corrosive environment can be expressed as mils (thousandths of an inch) per year penetration (MPY). 1 MPY is equal to 0.0254 mm/y, which is equal to 25.4 µm/y. The corrosion rate can be calculated with the assumption of uniform corrosion over the entire surface of the coupon. MPY can be calculated by multiplying the weight loss in grams by 22,300 and then dividing by the product of the area of coupon (sq. in.), the metal density of the coupon (g/cm3), and the time of exposure in a corrosive environment (days). Corrosion rate from metal loss can also be calculated as mm/y = 87.6 x (W/DAT) with W (weight loss in milligrams), D (metal density in g/cm3), A (area of sample in cm2), and T (time of exposure of the metal sample in hours).
  • Metal corrosion can occur via electrochemical reactions at the interface between a metal and an electrolyte solution. A thin film of moisture on a metal surface forms the electrolyte for atmospheric corrosion. Corrosion normally occurs at a rate determined by an equilibrium between opposing electrochemical reactions, anodic (metal oxidation) and cathodic (reduction of a solution species). These reactions can occur on one metal or on two or more dissimilar metals that are in electrical communication. Corrosion current can be used to generate a corrosion rate by assuming an electrolytic dissolution reaction involving a chemical species. Uniform corrosion across a metal surface allows calculation of the corrosion rate in units of distance per year. For an alloy undergoing uniform dissolution, equivalent weight is a weighted average of the equivalent weights of the alloy components. If the dissolution is not uniform, corrosion products can be used to calculate equivalent weight.
  • A weight loss can be converted to a corrosion rate with knowledge of the density and the sample area of a sample. ASTM Standard G 102, Standard Practice for Calculation of Corrosion Rates and Related Information from Electrochemical Measurements can be used. An eddy current instrument and probe can be used for measuring corrosion by monitoring a conductivity curve and impedance plane and using one or more techniques such as single layer corrosion detection, two layer corrosion detection, a limited penetration method, dual frequency method, and/or a variable frequency method.
  • The following examples are intended to illustrate, not limit, the present invention.
    • EXAMPLES Example 1
  • Copper metal sample coupons with a surface area of 3.38 in2 (21.8 cm2) were installed in a laboratory-scale liquid recirculating loop equipped with a reservoir capable of holding approximately 11 L total volume. The apparatus was designed to hold metal sample coupons in the path of flowing liquid at a chosen flow rate and temperature for chosen period of time. After exposure for an adequate period of time, the metal sample weight loss resulting from corrosion was used to calculate the corrosion rate. The exact conditions of the tests are listed in the Tables 1-3. For tests shown in all three tables, the temperature was 35°C, linear velocity was 7 gallons per minute (26.5 L/min, i.e. 3 ft/s or approximately 1 m/s), and the mass of treatment was 10 L. Synthetic water was used having 1170 ppm NaCl and 505 ppm NaHCO3, at pH 8.
  • For the purpose of evaluating yellow-metal corrosion inhibitor performance, corrosion rate data was generated for the trial material (hexylsulfamic acid) and a known industry corrosion inhibitor (tolyltriazole) (identified as "TTA" in the Tables) as a control, and in some cases untreated (blank) systems, using copper test coupons in sodium chloride-sodium bicarbonate brine at initial pH 8.8. This aqueous matrix was designed to mimic the pH, alkalinity, and total dissolved solids that might be found in a secondary treated municipal wastewater after four cycles of concentration. The inhibitor dosage range of from 5 ppm to 10 ppm was selected because this is an effective dosage range for the protection of copper with tolytriazole.
  • After exposure to the corrosive environment defined by the testing parameters, corrosion coupons were cleaned with an acidic solution that is capable of removing various chemical and biological deposits and films that might have formed on the coupon surface during exposure to the test environment. The weight change (and corresponding corrosion rate) determined before a coupon has been chemically cleaned helps the researcher ascertain general material removal and/or deposition process information. The corrosion rate obtained after cleaning is considered the true corrosion rate for the system under evaluation. Comparative data from known corrosion inhibitors and/or untreated systems collected at the time of the subject inhibitor evaluation are advantageous due to variability in experimental factors that otherwise are not easily controlled between different experiments. In the tables, the MPY (milli-inch per year) and µm/yr of corrosion were determined.
  • The data presented in Tables 1-3 show that hexylsulfamic acid has corrosion inhibitor properties that result in copper corrosion rates far less than that obtained in untreated systems. The data also show that the copper corrosion inhibition performance of hexylsulfamic acid is similar to that obtained for tolyltriazole. The data also show that hexylsulfamic acid performance as a copper corrosion inhibitor has an inverse relationship with inhibitor concentration under the given test conditions, which is similar to the performance trend obtained with tolyltriazole. Put another way, lower dosages, treatment levels, were more effective in controlling corrosion than higher dosages. TABLE 1
    Treatment Coupon Inhibitor Dosage ppm pH Weight Loss/Gain grams MPY µm/yr Time hours
    5ppm active TTA (before cleaning) Copper, CDA110 5 8.8 0.0009 0.025 0.635 649
    5ppm active TTA (after cleaning) Copper, CDA110 5 8.8 0.0043 0.118 3.00 649
    5ppm Hexyl Sulfamic Acid (before cleaning) Copper, CDA110 5 8.8 0.0009 0.025 0.635 649
    5ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 5 8.8 0.0043 0.118 3.00 649
    10ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 10 8.8 0.0068 0.186 4.72 649
    10ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 10 8.8 0.0214 0.586 14.9 649
    TABLE 2
    Treatment Coupon Inhibitor Dosage ppm pH Weight Loss/Gain grams MPY µm/yr Time hours
    Blank (before cleaning) Copper, CDA110 0 8.8 0.0086 0.097 2.46 1575
    Blank (after cleaning) Copper, CDA110 0 8.8 0.0188 0.212 5.38 1575
    5ppm active TTA (before cleaning) Copper, CDA110 5 8.8 0.0022 0.025 0.635 1575
    5ppm active TTA (after cleaning) Copper, CDA110 5 8.8 0.0056 0.063 1.60 1575
    10ppm Hexyl Sulfamic Acid (before cleaning) Copper, CDA110 10 8.8 0.0044 0.050 1.27 1575
    10ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 10 8.8 0.0111 0.125 3.18 1575
    TABLE 3
    Treatment Coupon Inhibitor Dosage ppm pH Weight Loss/Gain grams MPY µm/yr Time hours
    5ppm Hexyl Sulfamic Acid (before cleaning) Copper, CDA110 5 8.8 0.0018 0.174 4.42 184
    5ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 5 8.8 0.0055 0.531 13.49 184
    7.5ppm Hexyl Sulfamic Acid (before cleaning) Copper, CDA110 7.5 8.8 0.0036 0.348 8.84 184
    7.5ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 7.5 8.8 0.0089 0.860 21.84 184
    10ppm Hexyl Sulfamic Acid (before cleaning) Copper, CDA110 10 8.8 0.0033 0.319 8.10 184
    10ppm Hexyl Sulfamic Acid (after cleaning) Copper, CDA110 10 8.8 0.0097 0.937 23.80 184

Claims (15)

  1. A method of inhibiting corrosion of a metal surface comprising:
    applying at least one alkyl sulfamic acid or salt thereof to the metal surface in an amount of 1.0 to 50 ppm to inhibit corrosion of the metal surface, wherein the amount of the at least one alkyl sulfamic acid or salt thereof results in a lower degree of chemical change of the metal surface than in its absence.
  2. The method of claim 1, wherein the at least one alkyl sulfamic acid has the formula R1R2NS(O)2(OH), and
    R1 and R2 are independently a hydrogen, an alkyl group, or a cycloalkyl group, wherein the alkyl group is pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or neopentyl, and R1 and R2 are not both hydrogen.
  3. The method of claim 2, wherein R1 or R2, but not both, is an alkyl group or a cycloalkyl group, wherein the alkyl group is pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or neopentyl.
  4. The method of claim 2, wherein both R1 and R2 are an alkyl group or cycloalkyl group, wherein the alkyl group is pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or neopentyl.
  5. The method of claim 1, wherein the alkyl sulfamic acid or salt thereof is present in a fluid applied to the metal surface.
  6. The method of claim 5, wherein the fluid comprises at least one of H2O, NH3, and an alcohol.
  7. The method of claim 5, wherein the fluid comprises an acid or base in addition to the alkyl sulfamic acid or salt thereof.
  8. The method of claim 5, wherein the fluid comprises a salt solution of at least one salt independent of an alkyl sulfamic acid salt.
  9. The method of claim 1, wherein the applying comprises one or more of flowing, coating, sponging, wiping, spraying, painting, showering, and misting of the at least one alkyl sulfamic acid or salt thereof.
  10. The method of claim 1, wherein the applying comprises flowing a fluid comprising the at least one alkyl sulfamic acid or salt thereof over the metal surface.
  11. The method of claim 1, wherein the metal surface is a non-ferrous surface and preferably comprises copper or a copper-containing alloy.
  12. The method of claim 1, further comprising contacting the metal surface with at least one corrosive agent.
  13. The method of claim 1, wherein the metal surface is part of a closed fluid system.
  14. The method of claim 1, wherein the applying forms a protective film on the metal surface including the at least one alkyl sulfamic acid or salt thereof.
  15. The method of claim 1, wherein the at least one alkyl sulfamic acid or salt thereof is applied to the metal surface in an amount of 1.0 to 10 ppm.
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