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EP3916127B1 - Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques - Google Patents

Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques Download PDF

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Publication number
EP3916127B1
EP3916127B1 EP20176457.8A EP20176457A EP3916127B1 EP 3916127 B1 EP3916127 B1 EP 3916127B1 EP 20176457 A EP20176457 A EP 20176457A EP 3916127 B1 EP3916127 B1 EP 3916127B1
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EP
European Patent Office
Prior art keywords
corrosion
metals
metal
metallic surfaces
protection
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.)
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Application number
EP20176457.8A
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German (de)
English (en)
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EP3916127A1 (fr
EP3916127C0 (fr
Inventor
Andreas HEYN
Jan Johan Zwinselman
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.)
Aloxx GmbH
Otto Von Guericke Universitaet Magdeburg
Original Assignee
Aloxx GmbH
Otto Von Guericke Universitaet Magdeburg
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 Aloxx GmbH, Otto Von Guericke Universitaet Magdeburg filed Critical Aloxx GmbH
Priority to EP20176457.8A priority Critical patent/EP3916127B1/fr
Priority to PCT/EP2021/063804 priority patent/WO2021239685A1/fr
Priority to US17/998,749 priority patent/US20230203673A1/en
Publication of EP3916127A1 publication Critical patent/EP3916127A1/fr
Application granted granted Critical
Publication of EP3916127C0 publication Critical patent/EP3916127C0/fr
Publication of EP3916127B1 publication Critical patent/EP3916127B1/fr
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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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic 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
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids

Definitions

  • a corrosion inhibitor is used for protection of carbon steel in normal running processes, consisting of tungstate or molybdate, alkali or alkali earth metal gluconate, rare earth salt, zinc salt and stabilizer.
  • formulations often contain at least one critical chemical that lowers the environmentally friendliness.
  • Organic and/or inorganic zinc salts act as cathodic inhibitors, by reducing the corrosion rate due to retarding cathodic reactions.
  • cathodic inhibitors cause formation of insoluble compounds precipitating on the cathodic sites in form of a barrier film.
  • the effective cathode area is one of the factors of galvanic corrosion, therefore its reduction results in decrease of corrosion rate.
  • Zinc salts especially organic and/or inorganic zinc salts, can be kept dissolved in aqueous solutions by adding a chelating agent to the solution.
  • Amino acids and their salts, especially their metal salts, EDTA or various phosphorus-containing chemicals are well known chelating agents, used in compositions for corrosion inhibition of carbon steel.
  • organic zinc salts such as zinc gluconate, show promising effects on corrosion inhibition of carbon steel.
  • US 2014/0241939 A1 discloses a corrosion inhibition composition for cooling water applications made of carbon steel, comprising a carboxylic acid and its water-soluble salts in combination with Zn 2+ ions.
  • a water-soluble zinc salt such as zinc chloride, zinc sulphate or zinc oxide, is added to the cooling water system, in combination with a carboxylic acid, such as gluconic acid or saccharinic acid.
  • the concentration of the carboxylic acid in the cooling water is in the range 30 to 300 ppm.
  • Carboxylic acids with more than two carboxyl groups are not suitable.
  • US 4 512 915 A discloses a corrosion inhibition composition for metallic substrates, selected from Fe, Ni, Cu, Al or their alloys, in aqueous systems.
  • the composition comprises zinc gluconate or glucoheptonate and at least one inorganic polyphosphate, e.g. alkali metal hexamethaphosphate or -tripolyphosphate.
  • the optimized system comprises zinc gluconate and sodium hexametaphosphate 1:1 in a total concentration of 530 ppm in water.
  • the present invention provides the use of an environmentally friendly corrosion inhibition composition
  • an environmentally friendly corrosion inhibition composition comprising at least one zinc carboxylate and calcium gluconate, wherein the mass ratio of the at least one zinc carboxylate and the calcium gluconate is in the range of 1:10 to 1:600, for protecting of metals and/or metallic surfaces from corrosion.
  • Fig. 1 a) - e) depicts corrosion current densities (i corr ) in artificial tap water (see ASTM D1384-05) containing either no additive or 5% (w/w) calcium gluconate additive (the additive consisting of 5% (w/w) Ca-GDL and 95% (w/w) water) or 5% (w/w) additive A (the additive consisting of 4% (w/w) calcium gluconate, 1% (w/w) magnesium gluconate, 0.08% (w/w) zinc acetate and 94.92% (w/w) water) for a) mild steel, b) cast iron, c) zinc, d) aluminum and e) copper.
  • 5% (w/w) calcium gluconate additive the additive consisting of 5% (w/w) Ca-GDL and 95% (w/w) water
  • additive A the additive consisting of 4% (w/w) calcium gluconate, 1% (w/w) magnesium gluconate, 0.08%
  • the present invention provides an environmentally friendly corrosion inhibition composition for metallic surfaces comprising at least one zinc carboxylate and calcium gluconate, wherein the mass ratio of the at least one zinc carboxylate and the calcium gluconate is in the range of 1:10 to 1:600.
  • zinc salts are known to act as cathodic corrosion inhibitors for certain metals only, e.g. only for mild steel.
  • salts of carboxylic acids are known additives for the protection of metals from corrosion.
  • metal salts of carboxylic acids show an increased corrosion inhibition efficiency not only for steel, but for a broad variety of metals or metal alloys concurrently, when mixed h a combination according to the invention.
  • the corrosion inhibition composition for metallic surfaces comprises at least one zinc carboxylate and calcium gluconate.
  • carboxylate anion includes one or more kinds of carboxylate anions.
  • the carboxylate anions of the zinc carboxylate are selected from the group comprising gluconate, bisglycinate, glycinate, citrate, acetate, ascorbate, DL-hydrogenaspartate, L-hydrogenaspartate, malate and mixtures of these.
  • the zinc carboxylate is zinc gluconate.
  • the carboxylates are water-soluble and/or water-emulsifiable.
  • the range of possible concentrations of calcium gluconate within the liquid medium surrounding the metallic surface increases, when combined with a zinc carboxylate.
  • the mass ratio of the at least one zinc carboxylate and the calcium gluconate is in the range of 1:10 to 1:600, preferably in the range of 1:50 to 1:100.
  • a corrosion inhibition composition according to the present invention with said mass ratio shows constantly good results in corrosion inhibition for a broad variety of metals.
  • the corrosion inhibition composition according to the invention additionally comprises at least one magnesium carboxylate.
  • the corrosion inhibition composition according to the invention shows high corrosion inhibition efficiency for a wide range of metals and/or metallic surfaces concurrently.
  • metallic surface comprises surfaces of metals and/or metal alloys, as well as of any other metal and/or metal alloy containing material.
  • the concentration of the corrosion inhibition composition in the liquid medium is in the range of 0.01% to 50% (w/w), preferably in the range of 0.05% to 50% (w/w), more preferred in the range of 0.05% to 20% (w/w), regarding the total mass of the liquid formulation.
  • Another object of the invention is the use of a solid formulation comprising a composition according to the invention and at least one further component, wherein the at least one further component is selected from carrier materials, complexing agents, such as magnesium gluconate; softener and surfactants, for protection of metals and/or metallic surfaces from corrosion.
  • the at least one further component is selected from carrier materials, complexing agents, such as magnesium gluconate; softener and surfactants, for protection of metals and/or metallic surfaces from corrosion.
  • the corrosion inhibition composition, the liquid and/or solid formulation according to the invention is added to the liquid, the metallic surface is or will be exposed to, in an amount that the concentration of the corrosion inhibition composition in the liquid is in the range of 0.01% to 20% (w/w), more preferably in the range of 0.05% to 15% (w/w), most preferably in the range of 0.1% to 10% (w/w).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (13)

  1. Utilisation d'une composition inhibitrice de corrosion comprenant
    - au moins un carboxylate de zinc et
    - du gluconate de calcium,
    dans laquelle le rapport massique de l'au moins un carboxylate de zinc et du gluconate de calcium est dans la plage de 1:10 à 1:600,
    destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion,
    dans laquelle des surfaces métalliques comprennent des surfaces de métaux et/ou alliages métalliques, et de tout autre matériau contenant un métal et/ou alliage métallique.
  2. Utilisation d'une composition inhibitrice de corrosion destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion selon la revendication 1, dans laquelle l'anion carboxylate dans le carboxylate de zinc est choisi parmi le groupe comprenant gluconate, bisglycinate, glycinate, citrate, acétate, ascorbate, DL-hydrogène aspartate L-hydrogène aspartate, malate et leurs mélanges.
  3. Utilisation d'une composition inhibitrice de corrosion destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion selon la revendication 1 ou 2 comprenant en outre au moins un carboxylate de magnésium.
  4. Utilisation d'une composition inhibitrice de corrosion destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion selon l'une quelconque des revendications 1 à 3 comprenant en outre un agent chélatant.
  5. Utilisation d'une composition inhibitrice de corrosion destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion selon l'une quelconque des revendications 1 à 4, dans laquelle le métal dans la surface métallique est choisi parmi le groupe comprenant fonte, cuivre, aluminium, aluminium coulé, acier, acier doux, zinc, magnésium, magnésium coulé, étain, soudure, titane, laiton et leurs combinaisons.
  6. Utilisation selon l'une des revendications 1 à 5 destinée à protéger les métaux et/ou de surfaces métalliques contre la corrosion dans des liquides comprenant de l'eau.
  7. Procédé d'inhibition de la corrosion de métaux et/ou surfaces métalliques comprenant les étapes consistant à
    a) fournir une composition inhibitrice de corrosion comprenant
    - au moins un carboxylate de zinc et
    - du gluconate de calcium,
    dans lequel le rapport massique de l'au moins un carboxylate de zinc et du gluconate de calcium est dans la plage de 1:10 à 1:600, et
    b) ajouter la composition inhibitrice de corrosion à un milieu liquide,
    dans lequel le métal et/ou la surface métallique est ou sera exposé(e) au milieu liquide,
    dans lequel des surfaces métalliques comprennent des surfaces de métaux et/ou alliages métalliques, et de tout autre matériau contenant un métal et/ou alliage métallique.
  8. Procédé selon la revendication 6, dans lequel la concentration de la composition inhibitrice de corrosion dans le milieu liquide est dans la plage de 0,01 % à 20 % (p/p).
  9. Utilisation d'une formulation liquide comprenant une composition inhibitrice de corrosion selon l'une quelconque des revendications 1 à 5 et un milieu liquide, choisi parmi l'eau, au moins un solvant organique ou un mélange de ceux-ci pour la protection de métaux et/ou surfaces métalliques contre la corrosion, dans laquelle des surfaces métalliques comprennent des surfaces de métaux et/ou alliages métalliques, et de tout autre matériau contenant un métal et/ou alliage métallique.
  10. Utilisation d'une formulation liquide destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion selon la revendication 8, dans laquelle la concentration de la composition inhibitrice de corrosion est dans la plage de 0,01 % à 50 % (p/p) de la formulation liquide totale.
  11. Utilisation selon la revendication 9 et 10 pour la protection de métaux et/ou surfaces métalliques contre la corrosion dans des liquides comprenant de l'eau.
  12. Utilisation d'une formulation solide comprenant une composition inhibitrice de corrosion selon l'une quelconque des revendications 1 à 5 et au moins un autre composant,
    dans laquelle l'au moins un composant supplémentaire est choisi parmi des matériaux porteurs, agents complexants, émollients et agents tensioactifs,
    destinée à protéger les métaux et/ou surfaces métalliques contre la corrosion,
    dans laquelle des surfaces métalliques comprennent des surfaces de métaux et/ou alliages métalliques, et de tout autre matériau contenant un métal et/ou alliage métallique.
  13. Utilisation selon la revendication 12 pour la protection de métaux et/ou surfaces métalliques contre la corrosion dans des liquides comprenant de l'eau.
EP20176457.8A 2020-05-26 2020-05-26 Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques Active EP3916127B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20176457.8A EP3916127B1 (fr) 2020-05-26 2020-05-26 Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques
PCT/EP2021/063804 WO2021239685A1 (fr) 2020-05-26 2021-05-25 Utilisation d'une composition pour l'inhibition de la corrosion de métaux ou d'alliages métalliques et procédé d'inhibition de la corrosion de métaux ou d'alliages métalliques
US17/998,749 US20230203673A1 (en) 2020-05-26 2021-05-25 Use of a composition for inhibition of corrosion of metals or metal alloys and method for inhibition of corrosion of metals or metal alloys

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20176457.8A EP3916127B1 (fr) 2020-05-26 2020-05-26 Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques

Publications (3)

Publication Number Publication Date
EP3916127A1 EP3916127A1 (fr) 2021-12-01
EP3916127C0 EP3916127C0 (fr) 2024-07-03
EP3916127B1 true EP3916127B1 (fr) 2024-07-03

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EP20176457.8A Active EP3916127B1 (fr) 2020-05-26 2020-05-26 Composition et procédé permettant d'inhiber la corrosion des métaux ou d'alliages métalliques

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US (1) US20230203673A1 (fr)
EP (1) EP3916127B1 (fr)
WO (1) WO2021239685A1 (fr)

Family Cites Families (16)

* Cited by examiner, † Cited by third party
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GB1455247A (en) 1972-11-29 1976-11-10 Houseman Hegro Ltd Water treatment compositions
FR2512072A1 (fr) 1981-08-31 1983-03-04 Roquette Freres Composition et procede d'inhibition de la corrosion par l'eau des substrats metalliques
US5130052A (en) 1991-10-24 1992-07-14 W. R. Grace & Co.-Conn. Corrosion inhibition with water-soluble rare earth chelates
US5531931A (en) * 1994-12-30 1996-07-02 Cargill, Incorporated Corrosion-inhibiting salt deicers
US6764615B2 (en) 2001-05-21 2004-07-20 Cortec Corporation Migrating corrosion inhibitor fibers
US20040180807A1 (en) * 2002-12-30 2004-09-16 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for metal corrosion and rust formation protection
CN101485839A (zh) * 2008-01-16 2009-07-22 北京天科仁祥医药科技有限公司 一种用于防治小儿营养不良的中药制剂及其制备方法
CN101869142B (zh) * 2010-05-24 2012-05-30 北京世纪维他生物技术有限公司 干法配方奶粉用营养素预混料的生产方法
US8114344B1 (en) * 2010-12-21 2012-02-14 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions using sugar acids and Ca
CN102642934B (zh) 2012-04-23 2015-08-19 国家海洋局天津海水淡化与综合利用研究所 一种海水循环冷却水无磷环保型碳钢复合缓蚀剂及其制备和使用方法
US20140241939A1 (en) 2013-02-26 2014-08-28 Baker Hughes Incorporated Corrosion inhibitors for cooling water applications
CN104643190A (zh) * 2013-11-16 2015-05-27 周国萍 护肝保健饮料
CN104403523A (zh) 2014-12-16 2015-03-11 常熟市易安达电器有限公司 矿用喷雾杆
CN107829092A (zh) * 2017-12-26 2018-03-23 辽宁师范大学 一种绿色环保型碳钢缓蚀剂
CN108420025A (zh) * 2018-03-02 2018-08-21 宁夏中玺枣业股份有限公司 灵武长枣泡菜及制作方法

Also Published As

Publication number Publication date
US20230203673A1 (en) 2023-06-29
WO2021239685A1 (fr) 2021-12-02
EP3916127A1 (fr) 2021-12-01
EP3916127C0 (fr) 2024-07-03

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