EP0096619B1 - Corrosion-inhibiting means and compositions containing them - Google Patents

Corrosion-inhibiting means and compositions containing them Download PDF

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Publication number
EP0096619B1
EP0096619B1 EP83401050A EP83401050A EP0096619B1 EP 0096619 B1 EP0096619 B1 EP 0096619B1 EP 83401050 A EP83401050 A EP 83401050A EP 83401050 A EP83401050 A EP 83401050A EP 0096619 B1 EP0096619 B1 EP 0096619B1
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EP
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Prior art keywords
formula
compound
weight
aqueous
corrosion
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EP83401050A
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German (de)
French (fr)
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EP0096619A1 (en
Inventor
Francis Moran
Sylvain Rocher
Louis Cot
Francis Dabosi
Michel Duprat
Jean Les Hauts De L'arnel Durand
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Union Chimique Et Industrielle De L'ouest Sa SA
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Union Chimique Et Industrielle De L'ouest Sa SA
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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
    • 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
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic 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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds

Definitions

  • any metallic surface of current industrial use and that any material composed of one or more metals, such as iron and its alloys, in particular galvanized steel, copper and its alloys, aluminum and its alloys , to cite only the most used, are subjected, in contact with water, to corrosion phenomena which are all the more significant and cumulative as the additions of new water are themselves frequent, or significant in quantities in the installations, networks or devices using water as energy or thermal fluid.
  • metals such as iron and its alloys, in particular galvanized steel, copper and its alloys, aluminum and its alloys
  • an inhibiting composition comprising in combination (i) an orthophosphate, that is to say say a non-fluorinated phosphate, and (ii) a derivative of water-soluble organophosphonic acid or a polymer such as polyacrylamides, polyacrylic acids and polyacrylates.
  • the amount of fluorophosphate being such that, after introduction into the corrosive aqueous fluid, the content by weight of said fluorophosphate is between 3 and 500 ppm relative to the weight of said aqueous fluid.
  • the corrosion inhibiting means preferred according to the invention are the zinc and potassium fluorophosphates, namely ZnPO 3 F and K 2 PO 3 F, the most interesting means being ZnPO 3 F.
  • the fluorophosphates according to the invention are substances generally poorly water-soluble, the solubility threshold in water being of the order of 10 g / l.
  • the amines of formula I can be used as they can be obtained commercially, alone or mixed together, in their pure or technical forms.
  • polyamines sold which are suitable mention may in particular be made of the products known under the brand names DUOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN and CEMULCAT which contain at least one polyamine I.
  • DINORAM O Wood contains approximately 75% by dry weight of oleylamino-propylene-amine, 9% by dry weight of stearyllaminopropyleneamine and 6% by dry weight of hexadecylaminopropyleneamine
  • DINORAM S which contains approximately 43% by dry weight of stearyllaminopropyleneamine, 28 % by dry weight of oleylaminopropyleneamine and 28% by dry weight of hexadecylaminopropyleneamine, these products being marketed by the company CECA.
  • the polymeric organic polyelectrolytes having a molecular weight greater than or equal to approximately 150 and preferably a molecular weight greater than or equal to 300 are recommended.
  • the upper limit of the molecular weight can be very high and in particular of the order of 2,000,000 or more.
  • the polyelectrolytes which are suitable mention may in particular be made of the polymers and copolymers obtained from acrylic acid, its esters and its salts, methacrylic acid, its esters and its salts, acrylamide, methacrylamide, acid maleic, its esters and its salts.
  • these polyelectrolytes are polymeric substances obtained by polymerization, copolymerization or terpolymerization starting from a monomer which can be schematically represented by the formula wherein M 1, M 2, M 3 or M 4, which may be identical or different, each represent hydrogen, alkyl Cl-C4, nitrile, aldehyde, alcohol, amine, amide, imine , imide, ammonium, CO 2 M or SO 3 M (where M is H, C 1 -C 4 alkyl, NH 4 + or a metal cation, in particular Na + or K + ).
  • the definitions given above for the formula II include the copolymers obtained from ethylene and its ethylenic analogs (M i , M 2 , M 3 and M 4 each representing H or alkyl).
  • M i , M 2 , M 3 and M 4 each representing H or alkyl.
  • the acrylic, acrylate, acrylamide, acrylaldehyde, acrylonitrile, maleic type it is clear that at least one of the M 1 , M 2 , M 3 and M 4 is different from H and from the group alkyl C l -C 4 alkyl, in the formula of monomer II.
  • copolymer derivatives of the acrylic-acrylamic type schematically presenting a pattern (where R 1 , R 3 and R 4 are defined as above, n 2 is an integer greater than or equal to 1 and n 3 and n 4 , identical or different, are whole numbers greater than or equal to 1, a only of n 3 and n 4 which, in the case of a block copolymer, represent 0) and their mixtures;
  • aminoalkylenephosphonic and alkylene polyphosphonic acid derivatives which are suitable, mention may in particular be made of the acids of formula III.1, III.2 and III.3 below, their esters and their salts, and their mixtures, namely:
  • aminoalkylene phosphonic acids of general formula (in which n 5 represents an integer between 0 and 4 and n 6 represents an integer between 1 and 6), their salts with mono- or polyvalent metal ions, such as Na + , K + , NH 4 + , one of the preferred products of formula 111.1 being sodium aminotrimethylenephosphonate (where n 5 is 0);
  • alkylenediphosphonic acids such as in particular 1-hydroxyethylidene-1,1-diphosphonic acid of formula and its sodium, potassium or ammonium salts;
  • aminoalkylene polyphosphonic acids of formula where (Alk is a C1-C6 alkylene group and n 7 is an integer between 0 and 3), their metal or ammonium salts.
  • the products of Examples 1 and 2 are put into the form of aqueous compositions by suspending ZnPO 3 F or K 2 PO 3 F in water; use a composition containing 12 g / l of ZnPO 3 F or K 2 PO 3 F which is diluted at the time of use in the corrosive medium.
  • the products of Examples 3-7 are prepared by introducing ZnPO 3 F into the mixture of the other two means, said mixture having been obtained according to the methods described in the European patent and the European patent application mentioned above.
  • the products of Examples 8-10 are prepared by introducing into water ZnP0 3 F or K 2 PO 3 F with polyacrylic acid or potassium aminotrimethylenephosphonate.
  • the products of Examples 1, 3 and 6 are injected into the annular space of an oil well made of pumping steel, pumping and pumping and having a length of 2500 meters, into the aqueous mud so that the content of the products of the said examples is between 20 and 150 ppm. It can be seen that the corrosion rate expressed in ⁇ m / year is considerably reduced with the products of Examples 1, 3 and 6 compared to the control (injection of aqueous mud only).

Abstract

This invention relates to a corrosion inhibitor for protecting metallic surfaces which are in contact with water, in particular circuits, apparatus and devices which use water as energetic or thermic fluid, said corrosion inhibitor being a fluorophosphate compound selected from the group consisting of: (i) compound of the formula M2IPO3F, xH2O (ii) compound of the formula LiMIPO3F, xH2O (iii) compound of the formula NaMIPO3F, xH2O (iv) compound of the formula MIIPO3F, xH2O (v) compound of the formula M2IMII(PO3F)2, xH2O (vi) compound of the formula MIPO2F2, xH2O (vii) compound of the formula MII(PO2F2)2, x H2O (wherein MI is Na, K, Rb, Cs or HN4; MII is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and x is an integer or a fractional number comprised between 0 and 6) and (viii) mixtures thereof.

Description

La présente invention a trait à un nouveau procédé d'inhibition de la corrosion aqueuse au moyen d'un inhibiteur appartenant à la famille des fluorophosphates, pour protéger les surfaces métalliques, notamment celles des installations et dispositifs utilisant de l'eau comme fluide énergétique ou thermique. L'invention a trait également à une composition renfermant cet inhibiteur de corrosion en association avec une ou plusieurs autres substances utiles dans le domaine de la protection vis-à-vis de la corrosion aqueuse.The present invention relates to a new process for inhibiting aqueous corrosion by means of an inhibitor belonging to the family of fluorophosphates, for protecting metallic surfaces, in particular those of installations and devices using water as energetic fluid or thermal. The invention also relates to a composition containing this corrosion inhibitor in combination with one or more other substances useful in the field of protection against aqueous corrosion.

On sait que toute surface métallique d'usage industriel courant, et que tout matériel composé d'un ou de plusieurs métaux, tels le fer et ses alliages, notamment l'acier galvanisé, le cuivre et ses alliages, l'aluminium et ses alliages, pour ne citer que les plus employés, sont soumis, au contact de l'eau, à des phénomènes de corrosion d'autant plus importants et cumulatifs que les apports d'eau nouvelle sont eux- mêmes fréquents, ou importants en quantités dans les installations, réseaux ou dispositifs utilisant de l'eau comme fluide énergétique ou thermique.It is known that any metallic surface of current industrial use, and that any material composed of one or more metals, such as iron and its alloys, in particular galvanized steel, copper and its alloys, aluminum and its alloys , to cite only the most used, are subjected, in contact with water, to corrosion phenomena which are all the more significant and cumulative as the additions of new water are themselves frequent, or significant in quantities in the installations, networks or devices using water as energy or thermal fluid.

On sait que, dans le passé, pour résoudre le problème de la protection de surfaces métalliques vis-à-vis de la corrosion, on a proposé un certain nombre de solutions techniques. Parmi les solutions techniques récentes et très efficaces on connaît celles préconisées dans EP-B-10 485 et dans EP-A-65 609 qui font appel à des compositions renfermant soit au moins une polyamine et au moins un dérivé d'acide alkylènephosphonique, soit au moins une polyamine et au moins un polyélectrolyte organique résultant de la polymérisation ou copolymérisation d'un monomère présentant un motif C = C.It is known that, in the past, to solve the problem of protecting metal surfaces against corrosion, a number of technical solutions have been proposed. Among the recent and very effective technical solutions are known those recommended in EP-B-10 485 and in EP-A-65 609 which use compositions containing either at least one polyamine and at least one derivative of alkylene phosphonic acid, or at least one polyamine and at least one organic polyelectrolyte resulting from the polymerization or copolymerization of a monomer having a unit C = C.

Parmi les solutions techniques plus anciennes et moins efficaces, on connaît celles préconisées par FR-A-2192192 et FR-A-2 231 777 qui mettent en oeuvre une composition inhibitrice comprenant en association (i) un orthophosphate, c'est-à-dire un phosphate non fluore, et (ii) un dérivé d'acide organophosphonique hydrosoluble ou un polymère tel que les polyacrylamides, acides polyacryliques et polyacrylates.Among the older and less effective technical solutions, there are those recommended by FR-A-2192192 and FR-A-2 231 777 which use an inhibiting composition comprising in combination (i) an orthophosphate, that is to say say a non-fluorinated phosphate, and (ii) a derivative of water-soluble organophosphonic acid or a polymer such as polyacrylamides, polyacrylic acids and polyacrylates.

On sait par ailleurs que les fluorophosphates (également désignés par l'expression « dérivés oxyfluorés du phosphore 5 •) sont des substances connues, notamment de FR-A-2 352 895, en tant que moyens de passivation de surfaces métalliques avant peinture. FR-A-2 352 895, qui (voir page 3, lignes 1-16) rappelle que la phosphatation (i) est une opération ayant pour but de protéger les surfaces en acier contre la corrosion, et (ii) n'est pas suffisante pour empêcher les pièces de rouiller, préconise avant peinture, en remplacement de la phosphatation et d'un traitement au moyen d'anhydride chromique, d'effectuer une phosphatation et un traitement avec un fluorophosphate.It is also known that fluorophosphates (also designated by the expression “oxyfluorinated phosphorus derivatives 5 •) are known substances, in particular from FR-A-2 352 895, as means of passivation of metal surfaces before painting. FR-A-2 352 895, which (see page 3, lines 1-16) recalls that phosphating (i) is an operation intended to protect steel surfaces from corrosion, and (ii) is not sufficient to prevent parts from rusting, recommends before painting, to replace phosphating and treatment with chromic anhydride, to carry out phosphating and treatment with a fluorophosphate.

Selon l'invention, on préconise une nouvelle solution technique, pour résoudre le problème de la protection de surfaces métalliques vis-à-vis de la corrosion aqueuse, qui fait appel à un nouveau procédé différent des procédés antérieurement connus dans le domaine de l'inhibition de la corrosion.According to the invention, a new technical solution is recommended, to solve the problem of protecting metal surfaces against aqueous corrosion, which calls for a new process different from the processes previously known in the field of corrosion inhibition.

Cette nouvelle solution technique est particulièrement avantageuse pour protéger vis-à-vis de la corrosion aqueuse les surfaces métalliques des installations, réseaux et dispositifs utilisant de l'eau liquide (eau brute, eau déminéralisée, eau synthétique, eau industrielle pouvant notamment contenir un antigel, eau salée telle que l'eau de mer, boue aqueuse notamment pour forage pétrolier, etc...) comme fluide énergétique ou thermique (circuits de refroidissement ou de chauffage).This new technical solution is particularly advantageous for protecting against metal corrosion the metallic surfaces of installations, networks and devices using liquid water (raw water, demineralized water, synthetic water, industrial water which may in particular contain an antifreeze. , salt water such as sea water, aqueous mud in particular for oil drilling, etc.) as an energy or thermal fluid (cooling or heating circuits).

Le nouveau procédé selon l'invention pour la protection de surfaces métalliques vis-à-vis de la corrosion aqueuse, notamment les surfaces métalliques des installations utilisant de l'eau comme fluide corrosif énergétique ou thermique, est caractérisé en ce que l'on introduit dans le fluide aqueux corrosif un inhibiteur de corrosion appartenant à la famille des fluorophosphates et choisi parmi l'ensemble constitué par

  • (i) les composés de formule M2 1PO3F, xH2O
  • (ii) les composés de formule LiMIP03F, xH20
  • (iii) les composés de formule NaMIP03F, xH20
  • (iv) les composés de formule M"P03F, xH20
  • (v) les composés de formule M2 1M11(PO3F)2, xH2O
  • (vi) les composés de formule M1PO2F2, xH2O, et
  • (vii) les composés de formule M11(PO2F2)2, xH2O,

dans lesquelles M' est Na, K, Rb, Cs ou NH4 ; M11 est Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni ou Co ; et, X est un nombre entier ou fractionnaire compris entre 0 et 6, et,The new process according to the invention for the protection of metallic surfaces against aqueous corrosion, in particular the metallic surfaces of installations using water as corrosive energetic or thermal fluid, is characterized in that one introduces in the corrosive aqueous fluid a corrosion inhibitor belonging to the family of fluorophosphates and chosen from the group consisting of
  • (i) the compounds of formula M 2 1 PO 3 F, xH 2 O
  • (ii) the compounds of formula LiM I P0 3 F, xH 2 0
  • (iii) the compounds of formula NaM I P0 3 F, xH 2 0
  • (iv) the compounds of formula M "P0 3 F, xH 2 0
  • (v) the compounds of formula M 2 1 M 11 (PO 3 F) 2 , xH 2 O
  • (vi) the compounds of formula M 1 PO 2 F 2 , xH 2 O, and
  • (vii) the compounds of formula M 11 (PO 2 F 2 ) 2 , xH 2 O,

in which M 'is Na, K, Rb, Cs or NH 4 ; M 11 is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and, X is an integer or fractional number between 0 and 6, and,

(viii) leurs mélanges, la quantité de fluorophosphate étant telle que, après introduction dans le fluide aqueux corrosif la teneur en poids dudit fluorophosphate soit comprise entre 3 et 500 ppm par rapport au poids dudit fluide aqueux.(viii) their mixtures, the amount of fluorophosphate being such that, after introduction into the corrosive aqueous fluid, the content by weight of said fluorophosphate is between 3 and 500 ppm relative to the weight of said aqueous fluid.

Les moyens inhibiteurs de corrosion préférés selon l'invention sont les fluorophosphates de zinc et de potassium, à savoir ZnPO3F et K2PO3F, le moyen le plus intéressant étant ZnPO3F.The corrosion inhibiting means preferred according to the invention are the zinc and potassium fluorophosphates, namely ZnPO 3 F and K 2 PO 3 F, the most interesting means being ZnPO 3 F.

Les fluorophosphates selon l'invention sont des substances en général peu hydrosolubles, le seuil de solubilité dans l'eau étant de l'ordre de 10 g/I.The fluorophosphates according to the invention are substances generally poorly water-soluble, the solubility threshold in water being of the order of 10 g / l.

Cette faible hydrosolubilité n'est pas gênante eu égard aux quantités à utiliser. On a en effet observé que pour protéger les surfaces métalliques vis-à-vis de la corrosion aqueuse, qu'il convient d'utiliser une dose de 3 à 500 ppm de moyen inhibiteur selon l'invention, et de préférence une dose comprise entre 5 et 200 ppm notamment pour ZnPO3F, A ce sujet, il est signalé que par rapport aux eaux brute A et synthétique B décrites ci-après, la dose de ZnP03F donnant une inhibition maximale est de 20 à 25 ppm (voir tableau III ci-après).This low water solubility is not a problem with the amounts to be used. It has in fact been observed that, in order to protect the metal surfaces from aqueous corrosion, it is advisable to use a dose of 3 to 500 ppm of inhibitor means according to the invention, and preferably a dose of between 5 and 200 ppm in particular for ZnPO 3 F, In this regard, it is reported that compared to raw water A and synthetic B described below, the dose of ZnP0 3 F giving maximum inhibition is 20 to 25 ppm (see Table III below).

Selon un autre aspect de l'invention, on préconise une composition inhibitrice de corrosion comprenant, en association dans de l'eau :

  • A) un moyen inhibiteur de corrosion choisi parmi l'ensemble des fluorophosphates tel que défini ci-dessus, et
  • B) une substance choisie parmi l'ensemble constitué par les polyamines, les polyélectrolytes organiques résultant de la polymérisation ou copolymérisation d'un monomère présentant un motif C = C, les dérivés d'acide alkylènepolyphosphonique, les dérivés d'acide aminoalkylènephosphonique et leurs mélanges.
According to another aspect of the invention, a corrosion inhibiting composition is recommended comprising, in association in water:
  • A) a corrosion inhibitor means chosen from all of the fluorophosphates as defined above, and
  • B) a substance chosen from the group consisting of polyamines, organic polyelectrolytes resulting from the polymerization or copolymerization of a monomer having a C = C motif, alkylene polyphosphonic acid derivatives, aminoalkylene phosphonic acid derivatives and mixtures thereof .

Par rapport à l'utilisation des moyens A et B seuls, l'association de A et de B présente une synergie en ce qui concerne l'inhibition de la corrosion.Compared to the use of means A and B alone, the association of A and B presents a synergy as regards the inhibition of corrosion.

Parmi les substances B utilisables, on peut faire appel aux moyens décrits dans le brevet européen et la demande de brevet européen précités et à leurs mélanges.Among the substances B which can be used, use may be made of the means described in the aforementioned European patent and European patent application and in their mixtures.

Parmi les polyamines qui conviennent, on préconise celles qui répondent à la formule générale

Figure imgb0001
(où R représente un radical hydrocarboné aliphatique saturé ou insaturé en C12-C22, m représente un nombre entier compris entre 2 et 8 inclus et n représente un nombre entier compris entre 1 et 7 inclus, et leurs mélanges.Among the polyamines which are suitable, those which correspond to the general formula are recommended.
Figure imgb0001
 (where R represents a saturated or unsaturated C 12 -C 22 aliphatic hydrocarbon radical, m represents an integer between 2 and 8 inclusive and n represents an integer between 1 and 7 inclusive, and their mixtures.

Les amines de formule I peuvent être utilisées telles qu'on peut les obtenir dans le commerce, seules ou mélangées entre elles, sous leurs formes pures, ou techniques. On peut également utiliser des polyamines préparées à partir d'acides gras d'origine animale, végétale ou de synthèse. Parmi les polyamines commercialisées qui conviennent, on peut notamment citer les produits connus sous les noms de marque DUOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN et CEMULCAT qui renferment au moins une polyamine I. Parmi ces derniers produits, on peut mentionner le « DINORAM O » qui renferme approximativement 75 % en poids sec d'oléylamino-propylène-amine, 9 % en poids sec de stéarylaminopropylèneamine et 6 % en poids sec d'hexadécylaminopropylèneamine, le « DINORAM S qui renferme approximativement 43 % en poids sec de stéarylaminopropylèneamine, 28 % en poids sec d'oléylaminopropylèneamine et 28 % en poids sec d'hexadécylaminopropylèneamine, ces produits étant commercialisés par la société CECA.The amines of formula I can be used as they can be obtained commercially, alone or mixed together, in their pure or technical forms. One can also use polyamines prepared from fatty acids of animal, vegetable or synthetic origin. Among the polyamines sold which are suitable, mention may in particular be made of the products known under the brand names DUOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN and CEMULCAT which contain at least one polyamine I. Among these latter products, mention may be made of "DINORAM O "Which contains approximately 75% by dry weight of oleylamino-propylene-amine, 9% by dry weight of stearyllaminopropyleneamine and 6% by dry weight of hexadecylaminopropyleneamine," DINORAM S which contains approximately 43% by dry weight of stearyllaminopropyleneamine, 28 % by dry weight of oleylaminopropyleneamine and 28% by dry weight of hexadecylaminopropyleneamine, these products being marketed by the company CECA.

Parmi les polyélectrolytes pouvant être utilisés en tant que substances B, on préconise les polyélectrolytes organiques polymériques ayant un poids moléculaire supérieur ou égal à environ 150 et de préférence un poids moléculaire supérieur ou égal à 300. La limite supérieure du poids moléculaire peut être très élevée et notamment de l'ordre de 2 000 000 ou plus. Parmi les polyélectrolytes qui conviennent, on peut notamment mentionner les polymères et copolymères obtenus à partir de l'acide acrylique, ses esters et ses sels, l'acide méthacrylique, ses esters et ses sels, l'acrylamide, le méthacrylamide, l'acide maléique, ses esters et ses sels.Among the polyelectrolytes which can be used as substances B, the polymeric organic polyelectrolytes having a molecular weight greater than or equal to approximately 150 and preferably a molecular weight greater than or equal to 300 are recommended. The upper limit of the molecular weight can be very high and in particular of the order of 2,000,000 or more. Among the polyelectrolytes which are suitable, mention may in particular be made of the polymers and copolymers obtained from acrylic acid, its esters and its salts, methacrylic acid, its esters and its salts, acrylamide, methacrylamide, acid maleic, its esters and its salts.

D'une manière générale, ces polyélectrolytes sont des substances polymères obtenues par polymérisation, copolymérisation ou terpolymérisation à partir d'un monomère pouvant être schématiquement représenté par la formule

Figure imgb0002
dans laquelle M1, M2, M3 ou M4, qui peuvent être identiques ou différents, représentent chacun l'atome d'hydrogène, un groupe alkyle en CI-C4, nitrile, aldéhyde, alcool, amine, amide, imine, imide, ammonium, CO2M ou SO3M (où M est H, alkyle en C1-C4, NH4 + ou un cation métallique, notamment Na+ ou K+).In general, these polyelectrolytes are polymeric substances obtained by polymerization, copolymerization or terpolymerization starting from a monomer which can be schematically represented by the formula
Figure imgb0002
 wherein M 1, M 2, M 3 or M 4, which may be identical or different, each represent hydrogen, alkyl Cl-C4, nitrile, aldehyde, alcohol, amine, amide, imine , imide, ammonium, CO 2 M or SO 3 M (where M is H, C 1 -C 4 alkyl, NH 4 + or a metal cation, in particular Na + or K + ).

Les définitions données ci-dessus pour la formulle Il englobent les copolymères obtenus à partir de l'éthylène et de ses analogues éthyléniques (Mi, M2, M3 et M4 représentant chacun H ou alkyle). Cependant, pour obtenir notamment des polymères et copolymère du type acrylique, acrylate, acrylamide, acrylaldéhyde, acrylonitrile, maléique, II est clair qu'au moins un des M1, M2, M3 et M4 soit différent de H et du groupe alkyle en Cl-C4, dans la formule du monomère II.The definitions given above for the formula II include the copolymers obtained from ethylene and its ethylenic analogs (M i , M 2 , M 3 and M 4 each representing H or alkyl). However, to obtain in particular polymers and copolymers of the acrylic, acrylate, acrylamide, acrylaldehyde, acrylonitrile, maleic type, it is clear that at least one of the M 1 , M 2 , M 3 and M 4 is different from H and from the group alkyl C l -C 4 alkyl, in the formula of monomer II.

Les polyélectrolytes préférés ont été mentionnés ci-après, à savoir :The preferred polyelectrolytes have been mentioned below, namely:

(i) les dérivés du type polyacrylique répondant à la formule générale

Figure imgb0003
(où R1 est H, alkyle en C1-C4, Na+, K+ ou NH4 +, R2 est H ou alkyle en C1-C4 et n1 est un nombre entier supérieur ou égal à 2) et leurs mélanges ;(i) derivatives of the polyacrylic type corresponding to the general formula
Figure imgb0003
 (where R 1 is H, C 1 -C 4 alkyl, Na + , K + or NH 4 + , R 2 is H or C 1 -C 4 alkyl and n 1 is an integer greater than or equal to 2) and their mixtures;

(ii) les dérivés du type polymaléique répondant à la formule générale

Figure imgb0004
(où R3 et R4, qui peuvent être identiques ou différents, représentent chacun l'atome d'hydrogène ou un groupe alkyle en C1-C4, et R1 et n1 sont définis comme indiqué ci-dessus) et leurs mélanges ;(ii) derivatives of the polymaleic type corresponding to the general formula
Figure imgb0004
 (where R 3 and R 4 , which may be the same or different, each represents a hydrogen atom or a C 1 -C 4 alkyl group, and R 1 and n 1 are defined as indicated above) and their mixtures;

(iii) les dérivés du type polyacrylamide répondant à la formule générale

Figure imgb0005
(où R2 et n, sont définis comme indiqué ci-dessus) et leurs mélanges ;(iii) derivatives of the polyacrylamide type corresponding to the general formula
Figure imgb0005
 (where R 2 and n, are defined as indicated above) and their mixtures;

(iv) les dérivés copolymères du type acrylique-acrylamique présentant schématiquement un motif

Figure imgb0006
(où R1, R3 et R4 sont définis comme ci-dessus, n2 est un nombre entier supérieur ou égal à 1 et n3 et n4, identiques ou différents, sont des nombres entiers supérieurs ou égaux à 1, un seul des n3 et n4 pouvant, dans le cas d'un copolymère séquencé, représenter 0) et leurs mélanges ;(iv) copolymer derivatives of the acrylic-acrylamic type schematically presenting a pattern
Figure imgb0006
 (where R 1 , R 3 and R 4 are defined as above, n 2 is an integer greater than or equal to 1 and n 3 and n 4 , identical or different, are whole numbers greater than or equal to 1, a only of n 3 and n 4 which, in the case of a block copolymer, represent 0) and their mixtures;

(v) les dérivés copolymères du type styrène-maléique présentant schématiquement un motif

Figure imgb0007
(où R1, n2, n3 et n4 sont définis comme indiqué ci-dessus) et leurs mélanges ;(v) the copolymer derivatives of the styrene-maleic type having schematically a motif
Figure imgb0007
 (where R 1 , n 2 , n 3 and n 4 are defined as indicated above) and their mixtures;

(vi) les dérivés copolymères du type acrylique-acrylaamide présentant schématiquement un motif

Figure imgb0008
(où R1, R3, R4, n2, n3 et n4 sont définis comme indiqué ci-dessus) et leurs mélanges.(vi) the copolymer derivatives of the acrylic-acrylaamide type having schematically a pattern
Figure imgb0008
 (where R 1 , R 3 , R 4 , n 2 , n 3 and n 4 are defined as indicated above) and their mixtures.

Parmi les dérivés d'acide aminoalkylènephosphonique et alkylènepolyphosphonique qui conviennent, on peut notamment mentionner les acides de formule III.1, III.2 et III.3 ci-après, leurs esters et leurs sels, et leurs mélanges, à savoir :Among the aminoalkylenephosphonic and alkylene polyphosphonic acid derivatives which are suitable, mention may in particular be made of the acids of formula III.1, III.2 and III.3 below, their esters and their salts, and their mixtures, namely:

(i) les acides aminoalkylènephosphoniques de formule générale

Figure imgb0009
(dans laquelle n5 représente un nombre entier compris entre 0 et 4 et n6 représente un nombre entier compris entre 1 et 6), leurs sels avec des ions métalliques mono- ou polyvalents, tels que Na+, K+, NH4 +, l'un des produits préférés de formule 111.1 étant l'aminotriméthylènephosphonate de sodium (où n5 est 0) ;(i) aminoalkylene phosphonic acids of general formula
Figure imgb0009
 (in which n 5 represents an integer between 0 and 4 and n 6 represents an integer between 1 and 6), their salts with mono- or polyvalent metal ions, such as Na + , K + , NH 4 + , one of the preferred products of formula 111.1 being sodium aminotrimethylenephosphonate (where n 5 is 0);

(ii) les acides alkylènediphosphoniques, leurs esters et leurs sels, tels que notamment l'acide 1-hydroxyéthylidène-1,1-diphosphonique de formule

Figure imgb0010
et ses sels de sodium, potassium ou d'ammonium ; et(ii) alkylenediphosphonic acids, their esters and their salts, such as in particular 1-hydroxyethylidene-1,1-diphosphonic acid of formula
Figure imgb0010
 and its sodium, potassium or ammonium salts; and

(iii) les acides aminoalkylènepolyphosphoniques de formule

Figure imgb0011
où (Alk est un groupe alkylène en Ci-Ce et n7 est un nombre entier compris entre 0 et 3), leurs sels métalliques ou d'ammonium.(iii) aminoalkylene polyphosphonic acids of formula
Figure imgb0011
 where (Alk is a C1-C6 alkylene group and n 7 is an integer between 0 and 3), their metal or ammonium salts.

On a consigné dans le tableau 1 ci-après un certain nombre d'exemples de moyens inhibiteurs de corrosion aqueuse selon l'invention. Ces exemples nullement limitatifs sont donnés à titre d'illustration.

Figure imgb0012
Figure imgb0013
 A number of examples of means for inhibiting aqueous corrosion according to the invention have been recorded in table 1 below. These nonlimiting examples are given by way of illustration.
Figure imgb0012
Figure imgb0013

Les produits des exemples 1 et 2 sont mis sous forme de compositions aqueuses par mise en suspension de ZnPO3F ou K2PO3F dans de l'eau ; on utilisera une composition renfermant 12g/l de ZnPO3F ou K2PO3F que l'on dilue au moment de l'emploi dans le milieu corrosif. Les produits des exemples 3-7 sont préparés en introduisant ZnPO3F dans le mélange des deux autres moyens, ledit mélange ayant été obtenu selon les modalités décrites dans le brevet européen et la demande de brevet européen précités. Les produits des exemples 8-10 sont préparés en introduisant dans de l'eau ZnP03F ou K2PO3F avec l'acide polyacrylique ou l'aminotriméthylènephosphonate de potassium.The products of Examples 1 and 2 are put into the form of aqueous compositions by suspending ZnPO 3 F or K 2 PO 3 F in water; use a composition containing 12 g / l of ZnPO 3 F or K 2 PO 3 F which is diluted at the time of use in the corrosive medium. The products of Examples 3-7 are prepared by introducing ZnPO 3 F into the mixture of the other two means, said mixture having been obtained according to the methods described in the European patent and the European patent application mentioned above. The products of Examples 8-10 are prepared by introducing into water ZnP0 3 F or K 2 PO 3 F with polyacrylic acid or potassium aminotrimethylenephosphonate.

De façon avantageuse, quand on utilisera une composition renfermant un moyen A et une substance B, on fera appel à une composition comprenant :

  • 1 à 15 parties en poids sec de moyen A, et
  • 1 à 100 parties en poids sec de substance B.
Advantageously, when a composition containing a means A and a substance B is used, a composition comprising:
  • 1 to 15 parts by dry weight of medium A, and
  • 1 to 100 parts by dry weight of substance B.

On a résumé ci-après les essais qui ont été réalisés avec les produits selon l'invention.The tests which have been carried out with the products according to the invention have been summarized below.

I. Mesure directe de la corrosion par détermination de la perte de poids d'éprouvettes.I. Direct measurement of corrosion by determining the weight loss of test pieces.

a) Matériel et protocolea) Material and protocol

Le matériel et le protocole relatifs à la détermination de la perte de poids des éprouvettes par une mesure directe du type gravimétrique, sont ceux décrits dans le brevet européen précité EP-B-10485.The equipment and the protocol relating to the determination of the weight loss of the test pieces by a direct measurement of the gravimetric type, are those described in the aforementioned European patent EP-B-10485.

Les essais ont été entrepris sur des éprouvettes en acier, en cuivre et/ou en aluminium avec une eau brute « A (eau de forage) et une eau synthétique « B » très corrosive du fait de la présence de chlorures et d'oxygène dissous obtenue par déminéralisation totale de l'eau brute « A par passage sur résines échangeuses d'ions puis ajout de 200 mg/I de chlorure de sodium. Les eaux A et B avaient les caractéristiques suivantes données dans le tableau Il.

Figure imgb0014
Figure imgb0015
 The tests were undertaken on steel, copper and / or aluminum specimens with raw water "A (drilling water) and synthetic water" B "very corrosive due to the presence of chlorides and dissolved oxygen. obtained by total demineralization of the raw water “A by passage over ion exchange resins then addition of 200 mg / I of sodium chloride. Waters A and B had the following characteristics given in Table II.
Figure imgb0014
Figure imgb0015

La mesure de la perte de poids a été réalisé dans des essais du type « chauffage et du type « refroidissement ». Pour simplifier la lecture des résultats, la perte de poids a été traduite en vitesse de corrosion V (exprimée en µm/an) et en efficacité inhibitrice E % (pourcentage d'inhibition) selon les relations

Figure imgb0016
dans laquelle

  • V = vitesse de corrosion en µm/an,
  • P = perte de poids en mg,
  • J = nombre de jours d'exposition au milieu agressif,
  • S = surface externe de l'éprouvette en µm2,
  • d = masse spécifique du métal de l'éprouvette en mg/µm3 ; et
    Figure imgb0017
    dans laquelle Vo et V représentent respectivement les vitesses de corrosion (exprimées en µm/an) sans et avec inhibiteur.
The measurement of the weight loss was carried out in tests of the “heating” type and of the “cooling” type. To simplify the reading of the results, the weight loss has been translated into corrosion rate V (expressed in μm / year) and into inhibitory efficiency E% (percentage of inhibition) according to the relationships
Figure imgb0016
 in which
  • V = corrosion rate in µm / year,
  • P = weight loss in mg,
  • D = number of days of exposure to the aggressive medium,
  • S = external surface of the test piece in µm 2 ,
  • d = specific mass of the metal of the test piece in mg / µm 3 ; and
    Figure imgb0017
     in which Vo and V represent respectively the corrosion rates (expressed in µm / year) without and with inhibitor.

b) Résultatsb) Results

Les résultats obtenus ont été consignés dans les tableaux III, IV et V ci-après.The results obtained have been reported in Tables III, IV and V below.

Ces résultats montrent que les fluorophosphates selon l'invention et leurs associations avec des polyamines, des dérivés d'acide aminoalkylènepolyphosphoniques, et/ou des polyélectrolytes organiques inhibent de façon très efficace la corrosion aqueuse de surfaces métalliques.
(Voir tableau lll page 8)

Figure imgb0018
Figure imgb0019
Figure imgb0020
 These results show that the fluorophosphates according to the invention and their associations with polyamines, aminoalkylene polyphosphonic acid derivatives, and / or organic polyelectrolytes very effectively inhibit aqueous corrosion of metal surfaces.
(See table lll page 8)
Figure imgb0018
Figure imgb0019
Figure imgb0020

Il. Etude de l'inhibition de la corrosion aqueuse au moyen de ZnPO3F en fonction du pH.He. Study of the inhibition of aqueous corrosion using ZnPO 3 F as a function of pH.

Avec l'eau synthétique B décrite ci-dessus on a étudié l'inhibition de la corrosion aqueuse d'éprouvettes en acier au moyen de ZnP03F (produit de l'exemple 1) en fonction du pH. La technique de mesure de la perte de poids des éprouvettes, d'une part, et la détermination de la vitesse de corrosion et de l'efficacité anticorrosive, d'autre part, qui a été mise en oeuvre est celle utilisée ci-dessus.With the synthetic water B described above, the inhibition of aqueous corrosion of steel test pieces was studied by means of ZnP0 3 F (product of Example 1) as a function of the pH. The technique used to measure the weight loss of the test pieces, on the one hand, and the determination of the corrosion rate and the anticorrosive efficiency, on the other hand, which has been used is that used above.

Dans ces essais ZnPO3F a été utilisé à la dose de 25 ppm. Les résultats sont consignés dans le tableau VI.

Figure imgb0021
III. Inhibition de la corrosion d'un puits de forage pétrolier.In these tests ZnPO 3 F was used at a dose of 25 ppm. The results are reported in Table VI.
Figure imgb0021
 III. Inhibition of corrosion of an oil well.

On injecte dans l'espace annulaire d'un puits pétrolier en acier tonctionnant en pompage et ayant une longueur de 2500 mètres, les produits des exemples 1, 3 et 6 dans la boue aqueuse de façon que la teneur des produits desdits exemples soit comprise entre 20 et 150 ppm. On constate que la vitesse de corrosion exprimée en µm/an est considérablement diminuée avec les produits des exemples 1, 3 et 6 par rapport au témoin (injection de boue aqueuse seule).The products of Examples 1, 3 and 6 are injected into the annular space of an oil well made of pumping steel, pumping and pumping and having a length of 2500 meters, into the aqueous mud so that the content of the products of the said examples is between 20 and 150 ppm. It can be seen that the corrosion rate expressed in μm / year is considerably reduced with the products of Examples 1, 3 and 6 compared to the control (injection of aqueous mud only).

Claims (7)

1. A method for protecting metallic surfaces vis-a-vis water corrosion, in particular metallic surfaces of installations which use water as energetic or thermic corrosive fluid, said method being characterized in that into the aqueous corrosive fluid is introduced a corrosion inhibitor belonging to the fluorophosphates family and selected from the group consisting of :
(i) compound of the formula M2 1PO3 F. xH20
(ii) compound of the formula LiM1PO3F. xH2O
(iii) compound of the formula NaMIP03F. xH20
(iv) compound of the formula M11PO3F. xH2O
(v) compound of the formula M2 1M11(PO3F)2. xH2O
(vi) compound of the formula M1PO2F2. xH2O
(vii) compound of the formula M11(PO2F2)2. xH2O

(wherein M1 is Na, K, Rb, Cs or NH4 ; M11 is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co ; and x is an integer or a fractional number comprised between 0 and 6) and
(viii) mixtures thereof,

whereby, after introduction into the aqueous corrosive fluid, the fluorophosphate inhibitor amount is between 3 and 500 ppm by weight with respect to the weight of said aqueous fluid.
2. A method according to claim 1, characterized in that the inhibitor means is zinc fluorophosphate ZnP03F.
3. A method according to claim 1, characterized in that the inhibitor means is potassium fluorophosphate K2PO3F.
4. A method according to claim 1, characterized in that, after introduction into the aqueous corrosive fluid, the content of said fluorophosphate inhibitor is between 5 and 200 ppm by weight with respect to the weight of said aqueous fluid.
5. A method according to claim 1, characterized in that the fluorophosphate inhibitor is ZnP03F and that, after introduction into the aqueous corrosive fluid the content in said ZnP03F is between 5 and 200 ppm by weight with respect to the weight of said aqueous fluid.
6. A composition for inhibiting water corrosion characterized in that it comprises in association in water :
A) a corrosion inhibitor belonging to the fluorophosphates family according to claim 1, and
B) a substance selected from the group consisting of polyamines, organic polyelectrolytes resulting from polymerization and copolymerization of a monomer having a C = C double bond, alkylenepolyphosphonic acid derivatives, aminoalkylenephosphonic acid derivatives and mixtures thereof.
7. An aqueous anticorrosion composition according to claim 6, characterized in that it comprises :
from 1 to 15 parts by weight of means A, and
from 1 to 100 parts by weight of substance B.
EP83401050A 1982-05-28 1983-05-26 Corrosion-inhibiting means and compositions containing them Expired EP0096619B1 (en)

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