US10385460B2 - Composition and method for treating white rust - Google Patents

Composition and method for treating white rust Download PDF

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US10385460B2
US10385460B2 US14/819,726 US201514819726A US10385460B2 US 10385460 B2 US10385460 B2 US 10385460B2 US 201514819726 A US201514819726 A US 201514819726A US 10385460 B2 US10385460 B2 US 10385460B2
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water
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white rust
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Ecaterina Henderson
Lyle H. Steimel
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NCH Corp
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Priority to CA2956455A priority patent/CA2956455C/fr
Priority to PCT/US2015/044031 priority patent/WO2016022814A1/fr
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Assigned to THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT reassignment THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT SECURITY INTEREST Assignors: CHEM-AQUA, INC., NCH CORPORATION, NCH Life Sciences LLC
Assigned to THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT reassignment THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT SECURITY INTEREST Assignors: CHEM-AQUA, INC., DIVERSEY TASKI, INC., DIVERSEY, INC., INNOVATIVE WATER CARE, LLC, NCH CORPORATION, NCH Life Sciences LLC, SOLENIS TECHNOLOGIES, L.P.
Assigned to THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT reassignment THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT SECURITY INTEREST Assignors: CHEM-AQUA, INC., NCH CORPORATION, NCH Life Sciences LLC
Assigned to THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT reassignment THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT SECURITY INTEREST Assignors: CHEM-AQUA, INC., NCH CORPORATION, NCH Life Sciences LLC
Assigned to GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT reassignment GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT SECURITY INTEREST Assignors: CHEM-AQUA, INC., DIVERSEY, INC., INNOVATIVE WATER CARE, LLC, NCH CORPORATION, NCH Life Sciences LLC, SOLENIS TECHNOLOGIES, L.P.
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    • 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
    • C23F11/167—Phosphorus-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
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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

Definitions

  • Galvanized steel has a long history as an effective and economical material of construction for commercial and industrial water systems, including open loop, closed loop, recirculating, and once-through systems, such as cooling towers, chilled water systems, other evaporative cooling systems.
  • Galvanized steel consists of a thin coating of zinc fused to a steel substrate.
  • White rust is a rapid, localized corrosion attack on zinc that usually appears as a voluminous white deposit. This raid corrosion can completely remove zinc in a localized area with the resultant reduction in equipment life.
  • compositions for treating white rust particularly white rust on galvanized steel components in commercial and industrial water systems.
  • U.S. Pat. Nos. 5,407,597 and 6,468,470 disclose compositions comprising organophosphorus compounds (including 2-phosphonobutane-1,2,4-tricarboxylic acid, “PBTC”), an alkali metal salt of molybdenum, titanium, tungsten, or vanadium, and either a carbamate compound or a tannin compound.
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • U.S. Pat. No. 6,183,649 discloses a white-rust treatment composition comprising PBTC, sodium polyacrylate, sodium tolytriazole, an alkali metal molybdate, and an alkali metal bromide for treating circulating water systems.
  • the '649 patent also discloses the addition of a 1.5% aqueous solution of decyl thioethyletheramine (DTEA) at a rate of 25 lb/1,000 gallons of water/week to the circulating water system prior to adding the white rust treatment composition at a rate of 600 ppm per cycle for ten cycles of recirculation after addition of the DTEA.
  • DTEA decyl thioethyletheramine
  • U.S. Pat. No. 7,851,655 discloses white rust treatment compositions comprising various amine compounds, such as the reaction products of Jeffamine® (containing oxypropylene) with glycidol(2,3-epoxy-1-propanol).
  • U.S. Pat. No. 8,585,964 discloses a synergistic blend of 0-10% by weight of an amine-based white rust inhibitor (including those disclosed in the '655 patent) and 10-90% by weight of a benzotriazole.
  • the composition of the '964 may also include a fluorescent tracer to track dosage level.
  • U.S. Pat. No. 2,333,206 Another amine-based corrosion and white rust treatment is disclosed in U.S. Pat. No. 2,333,206.
  • the '206 patent is directed to treatment of metal surfaces in atmospheric conditions (rather than surfaces exposed to flowing water contact in an industrial water system) by applying acrylic, aliphatic amines to metal surfaces to provide a spread thickness of 10,000 to 80,000 sq. ft./lb of amines.
  • One of the amines disclosed in the '206 patent is 9,10-octadecenylamine.
  • an improved white rust inhibitor comprises a mixture of commerically available treatment products.
  • These commercially available products are Cetamine V217 S and Chem-Aqua 31155, which have previously been used to treat industrial and commerical water systems, but not previously used in combination as a treatment for white rust.
  • Cetamine V217 S is a liquid, all-organic product that prevents corrosion through film forming amines and neutralizing amines.
  • the corrosion inhibition of Cetamine V217 S is based on formation of a protective film by adsorption of the filming amine on the surface by its nitrogen atoms.
  • the stabilizing and dispersing effect of Cetamine V217 S prevents the formation of scale by blocking crystal growth.
  • Chem-Aqua 31155 is PBTC/Polymer/TTA blend used as a scale inhibitor in cooling towers.
  • Cetamine V217 S is used in concentrations of around 25-1000 ppm in combination with around 50-150 ppm for Chem-Aqua 31155. More preferably, Cetamine V217 S is used in concentrations of around 200-500 ppm in combination with around 100-150 ppm for Chem-Aqua 31155.
  • FIG. 1 is a photograph of a coupon before treatment and showing no white rust deposits
  • FIG. 2A is a photograph of a coupon after two days of treatment with only Chem-Aqua 31155 at 150 ppm;
  • FIG. 2B is a photograph of the coupon of FIG. 2A after one week of treatment
  • FIG. 2C is a photograph of the coupon of FIGS. 2A and 2B after two weeks of treatment;
  • FIG. 3A is a photograph of a coupon after two days of treatment with Cetamine V217S at 200 ppm and Chem-Aqua 31155 at 150 ppm;
  • FIG. 3B is a photograph of the coupon of FIG. 3A after one week of treatment
  • FIG. 3C is a photograph of the coupon of FIGS. 3A and 3B after two weeks of treatment;
  • FIG. 4A is a photograph of a coupon after two days of treatment with Cetamine V217S at 300 ppm and Chem-Aqua 31155 at 150 ppm;
  • FIG. 4B is a photograph of the coupon of FIG. 4A after one week of treatment
  • FIG. 4C is a photograph of the coupon of FIGS. 4A and 4B after two weeks of treatment
  • FIG. 5A is a photograph of a coupon after two days of treatment with Cetamine V217S at 500 ppm and Chem-Aqua 31155 at 150 ppm;
  • FIG. 5B is a photograph of the coupon of FIG. 5A after one week of treatment.
  • FIG. 5C is a photograph of the coupon of FIGS. 5A and 5B after two weeks of treatment.
  • the tests were run using two different water chemistries: low LSI (Langelier Saturation Index, the higher the LSI the more potential for white rust formation) corrosive water and water with hardness, having the properties listed below in Table 1.
  • a first test was run using only Chem-Aqua 31155 added to the containers of water at 150 ppm, and second-fourth tests were run with Chem-Aqua 31155 at 150 ppm and the white rust inhibitor Cetamine V217 S was added at various levels (200 ppm, 300 ppm, and 500 ppm, respectively) based on manufacturer recommendations.
  • the coupons Prior to adding the galvanized coupons to the containers with water, the coupons cleaned with a supersaturated ammonium acetate solution, followed by water and IPA (isopropyl alcohol) rinse. Coupon weight was recorded before use and after the cleaning and MPY (mils per year) corrosion rates were determined.
  • IPA isopropyl alcohol
  • FIG. 2A shows a coupon after two days of treatment with only Chem-Aqua 31155 at 150 ppm in a hard water container.
  • FIGS. 2B and 2C show the same coupon after 1 week and 2 weeks of treatment, respectively, with only Chem-Aqua 31155 in a hard water container.
  • White rust is visually manifested as white, fluffy sometimes “waxy” deposits on wetted galvanized steel. As can bee seen, the formation of white rust is visible after 2 days of treatment with CHem-Aqua 31155 at 150 ppm ( FIG. 2A ) and is extensive by 1 week ( FIG. 2B ). By the end of two weeks, the coupon is almost entirely covered with white rust as shown in FIG. 2C .
  • FIGS. 3A-3C show coupons after two days, 1 week, and 2 weeks, respectively, of treatment with Chem-Aqua 31155 at 150 ppm and Cetamine V217S at 200 ppm in a hard water container. Although there was some white rust formation after 2 days, the amount of white rust was less than on the coupon treated with only Chem-Aqua 31155 ( FIG. 2A ). The difference in white rust formation comparing the Chem-Aqua 31155 only treatment ( FIG. 2B ) to the combination of Cetamine V217 S and Chem-Aqua 31155 ( FIG. 3B ) after 1 week of treatment was even greater.
  • FIGS. 4A-4C similarly show coupons after two days, 1 week, and 2 weeks, respectively, of treatment with Chem-Aqua 31155 at 150 ppm and Cetamine V217S at 300 ppm in a hard water container.
  • Chem-Aqua 31155 at 150 ppm
  • Cetamine V217S at 300 ppm
  • the amount of white rust was less than on the coupon treated with only Chem-Aqua 31155.
  • the amount of white rust formation at two weeks is only slightly greater than at 1 week and the two-week level is far less than either the two-week level when Cetamine V217 S is used at a concentration of 200 ppm with Chem-Aqua 31155 at 150 ppm or when Chem-Aqua 31155 is used alone.
  • FIGS. 5A-5C similarly show coupons after two days, 1 week, and 2 weeks, respectively, of treatment with Chem-Aqua 31155 at 150 ppm and Cetamine V217S at 500 ppm in a hard water container. As can be seen, the results in preventing white rust formation are even better at these concentrations.
  • Chem-Aqua 31155 commerically available from Chem-Aqua, Inc., is a PTSA traced PBTC/PolymerITTA blend that is currently used for calcium carbonate scale control under high stress conditions and has a pH of 12.1. MSDS information for Chem-Aqua 31155 lists its ingredients as indicated in Tale 2 below.
  • Cetamine V217 S is commerically available from BK Giulini (BK Water Solutions) Germany and distributed by ICL Water Solutions. MSDS information for Cetamine V217 S indicates that it is a liquid, water soluble, all organic corrosion inhibitor for steam boilers with a pH or 1% solution of 10.0 have the primary ingredients listed in Table 3 below:
  • Oleylamine has the molecular formula C18H35NH2 and is also known as (Z)-Octa-9-decenylamine (CAS number 112-90-3) and is similar in structure to a fatty oleic acid.
  • the structure of oleylamine is shown below:
  • an improved white rust inhibitor comprises a mixture of a first composition (or component) and a second composition (or component).
  • the first composition preferably comprises around 2.5-10% 2-diethylaminoethanol (DEAE), around 2.5-5% cyclohexylamine at 2.5-5%, 0-2.5% oleylamine ((Z)-octadec-9-enylamine).
  • the second composition preferably comprises 40-60% DI water, 2-10% K-7028 (sodium polyacrylate), 10-20% NaOH 50% pt.
  • the second composition may comprise around 0.5-1.5% Spectra Trace SH-L or another flourescent tracer.
  • the white rust inhibitor comprises between 25-1000 ppm of the first composition and between 50-150 ppm of the second composition. Most preferably, the white rust inhibitor comprises between 200-500 ppm of the first composition and between 100-150 ppm of the second composition.
  • an improved white rust inhibitor comprises a combination of commerically available products: Cetamine V217 S and Chem-Aqua 31155.
  • the white rust inhibitor comprises between 25-1000 ppm of Cetamine V217 S and between 50-150 ppm of Chem-Aqua 31155.
  • the white rust inhibitor comprises between 200-500 ppm of Cetamine V217 S and between 100-150 ppm of Chem-Aqua 31155.
  • Water systems are treated by adding the composition according to the invention to achieve concentrations of treatment composition according to the above amounts. Periodic re-treatment may be needed to maintain concentration levels within the preferred treatment ranges.
  • Those of ordinary skill in the art will understand that the other suitable or equivalent chemical compounds may be substituted for any of the above ingredients within the scope of this invention.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)
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MX2017001696A MX384950B (es) 2014-08-08 2015-08-06 Composición y método para tratar óxido blanco.
US14/819,726 US10385460B2 (en) 2014-08-08 2015-08-06 Composition and method for treating white rust
CA2956455A CA2956455C (fr) 2014-08-08 2015-08-06 Composition et procede permettant le traitement de rouille blanche
PCT/US2015/044031 WO2016022814A1 (fr) 2014-08-08 2015-08-06 Composition et procédé permettant le traitement de rouille blanche
US15/870,260 US10280520B2 (en) 2014-08-08 2018-01-12 Composition and method for treating white rust

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US20160040301A1 (en) 2016-02-11
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